Process for treating and/or forming a non-newtonian fluid using microchannel process technology

ABSTRACT

The disclosed invention relates to a process, comprising: conducting unit operations in at least two process zones in a process microchannel to treat and/or form a non-Newtonian fluid, a different unit operation being conducted in each process zone; and applying an effective amount of shear stress to the non-Newtonian fluid to reduce the viscosity of the non-Newtonian fluid in each process zone, the average shear rate in one process zone differing from the average shear rate in another process zone by a factor of at least about 1.2.

This application is a continuation of U.S. application Ser. No.11/737,955 filed Apr. 20, 2007. This application claims priority under35 U.S.C. §119(e) to U.S. Provisional Application Ser. No. 60/793,519filed Apr. 20, 2006. The disclosures in these prior applications areincorporated herein by reference.

TECHNICAL FIELD

This invention relates to a process for treating and/or forming anon-Newtonian fluid using microchannel process technology.

BACKGROUND

Non-Newtonian fluids are liquids that exhibit viscosities that vary withchanging shear stress or shear rate. Non-Newtonian fluids may comprisepolymers, polymer solutions, emulsions, multiphase fluid mixtures, andthe like. These non-Newtonian fluids may be useful as pharmaceuticals,adhesives, food products, personal care products, coating compositions,and the like. A problem with treating non-Newtonian fluids inmicrochannels relates to the fact that when the non-Newtonian fluidsflow at high flow rates, high velocity gradients at the walls of themicrochannels are created. This leads to high apparent viscosities andhigh pressure drops within the microchannels. This invention, in atleast one embodiment, provides a solution to this problem.

SUMMARY

This invention relates to a process, comprising: conducting unitoperations in at least two process zones in a process microchannel totreat and/or form a non-Newtonian fluid, a different unit operationbeing conducted in each process zone; and applying an effective amountof shear stress to the non-Newtonian fluid to reduce the viscosity ofthe non-Newtonian fluid in each process zone, the average shear rate inone process zone differing from the average shear rate in anotherprocess zone by a factor of at least about 1.2. The shear rate in atleast one process zone may be is in excess of about 100 sec⁻¹, and inone embodiment in excess of about 1000 sec⁻¹.

The process microchannel may have a converging cross-sectional area inat least one process zone, and the shear stress may be applied to thenon-Newtonian fluid by flowing the non-Newtonian fluid through theconverging cross-sectional area.

The process microchannel may comprise surface features on and/or in oneor more interior surfaces in at least one process zone, and the shearstress may be applied to the non-Newtonian fluid by flowing thenon-Newtonian fluid in contact with the surface features.

The process microchannel may comprise one or more interior structuredwalls in at least one process zone, and the shear stress may be appliedto the non-Newtonian fluid by flowing the non-Newtonian fluid in contactwith one or more structured walls.

The process microchannel may comprise one or more internal obstructionsin at least one process zone, and the shear stress may be applied to thenon-Newtonian fluid by flowing the non-Newtonian fluid in contact withone or more internal obstructions.

The process microchannel may comprise a coating layer comprising voidsand/or protrusions on one or more of its interior surfaces in at leastone process zone, and the shear stress may be applied to thenon-Newtonian fluid by flowing the non-Newtonian fluid in contact withthe coating layer.

The unit operation in each process zone may comprise a chemicalreaction, chemical separation, condensation, vaporization, heating,cooling, compression, expansion, phase separation, mixing, or acombination of two or more thereof.

The same unit operation may occur in the two or more process zones.However, the channel geometry may be different to allow for a moreoptimized shear stress environment for the process fluid.

The unit operation in each process zone may comprise heating thenon-Newtonian fluid, cooling the non-Newtonian fluid, forming thenon-Newtonian fluid by mixing two or more fluids, contacting and/ormixing the non-Newtonian fluid with one or more other fluids and/orparticulate solids, conducting a reaction using two or more fluids toform a non-Newtonian fluid, conducting a reaction using as the reactantone or more non-Newtonian fluids, compressing the non-Newtonian fluid,expanding the non-Newtonian fluid, condensing the non-Newtonian fluid,vaporizing the non-Newtonian fluid, separating one or more componentsfrom the non-Newtonian fluid, or a combination of two or more thereof.

The viscosity of the non-Newtonian in at least one process zone fluidmay be reduced to a viscosity up to about 10⁵ centipoise during theinventive process.

BRIEF DESCRIPTION OF THE DRAWINGS

In the annexed drawings, like parts and features have like references. Anumber of the drawings are schematic illustrations which may not beaccurately proportional.

FIG. 1 is a schematic illustration of a microchannel that may be usefulin the inventive process.

FIG. 2 is a schematic illustration of an alternate embodiment of amicrochannel that may be useful in the inventive process. Thismicrochannel may be referred to as having a converging cross-sectionalarea.

FIG. 3 is a schematic illustration of a microchannel processing unitthat may be useful in treating a non-Newtonian fluid.

FIGS. 4-12 are schematic illustrations of microchannel repeating unitsthat may be used in the microchannel processing unit illustrated in FIG.3. These repeating units comprise a process microchannel and heatexchange channels, the heat exchange channels being adjacent to and inthermal contact with the process microchannels. (FIG. 7 shows twoadjacent process microchannels, and the heat exchange channels areadjacent to and in thermal contact with one of the process microchannelsand in thermal contact with the other process microchannel.) The processmicrochannels comprise internal surface features and/or convergingcross-sectional areas for applying shear stress to the non-Newtonianfluid. These repeating units may be used to exchange heat with thenon-Newtonian fluid. They may be used to conduct a chemical reactionusing a homogeneous catalyst, the non-Newtonian fluid being a reactantand/or product.

FIG. 13 is a schematic illustration of a microchannel repeating unitthat may be used in the microchannel processing unit illustrated in FIG.3. The repeating unit comprises a process microchannel, a stagedaddition channel, an apertured section positioned between the processmicrochannel and the staged addition channel, and heat exchangechannels. This repeating unit may be used for mixing an emulsion ormultiphase fluid mixture, or for conducting a chemical reaction using ahomogeneous catalyst.

FIG. 14 is a schematic illustration of an alternate embodiment of themicrochannel repeating unit illustrated in FIG. 13 wherein a firstrepeating section and a second repeating section are positioned adjacentto one another, the first repeating section comprising a first processmicrochannel, a first staged addition channel and a first aperturedsection, the second repeating section comprising a second processmicrochannel, second staged addition channel and second aperturedsection. Heat exchange channels are adjacent to and in thermal contactwith the first repeating section and in thermal contact with the secondrepeating section.

FIG. 15 is a schematic illustration of a repeating unit comprising aprocess microchannel and adjacent heat exchange channels. This repeatingunit may be used in the microchannel processing unit illustrated in FIG.3. The process microchannel contains a reaction zone comprising acatalyst. The interior walls of the process microchannel upstream of thecatalyst comprise surface features for applying shear stress to thenon-Newtonian fluid. The catalyst illustrated in FIG. 15 is in the formof a bed of particulate solids. However, any of the catalyst formsdiscussed in the specification may be used in the process microchannelillustrated in FIG. 15.

FIG. 16 is a schematic illustration of a repeating unit comprising aprocess microchannel and adjacent heat exchange channels that may beused in the microchannel processing unit illustrated in FIG. 3. Theprocess microchannel contains a reaction zone comprising a catalyst. Thecatalyst is positioned on one of the interior walls of the processmicrochannel. The interior wall of the process microchannel opposite thecatalyst comprises surface features for applying shear stress to thenon-Newtonian fluid.

FIG. 17 is a schematic illustration of a repeating unit that is similarto the repeating unit illustrated in FIG. 16 with the exception that theinterior wall of the process microchannel wherein the catalyst ismounted also includes surface features for applying shear stress to thenon-Newtonian fluid, these surface features being upstream of thecatalyst.

FIG. 18 is a schematic illustration of a repeating unit similar to therepeating unit illustrated in FIG. 17 with the exception that thesurface features that are downstream of the catalyst in FIG. 17 areexcluded in FIG. 18.

FIG. 19 is a schematic illustration of a repeating unit comprising aprocess microchannel and adjacent heat exchange channels that may beused in the microchannel processing unit illustrated in FIG. 3. Theprocess microchannel has a converging cross-sectional area. A catalystin the form of a bed of particulate solids is positioned in the processmicrochannel. However, any of the catalysts forms discussed in thespecification may be used in the process microchannel illustrated inFIG. 19.

FIG. 20 is a schematic illustration of a repeating unit that is similarto the repeating unit illustrated in FIG. 19 with the exception that theprocess microchannel includes two sections, one of the sections having aconverging cross-sectional area, and the other section having anon-converging cross-sectional area. The catalyst, which is in the formof a bed of particulate solids, is in the section of the processmicrochannel having the non-converging cross-sectional area.Alternatively, instead of being in the form of a bed of particulatesolids, the catalyst may have any of the forms discussed herein.

FIG. 21 is a schematic illustration of a repeating unit that is similarto the repeating unit illustrated in FIG. 20 with the exception that thecatalyst is in the section of the process microchannel having theconverging cross-sectional area.

FIG. 22 is a schematic illustration of a repeating unit that is similarto the repeating unit illustrated in FIG. 20 with the exception that thecatalyst is positioned partly in the section having the convergingcross-sectional area and partly in the section having the non-convergingcross-sectional area.

FIG. 23 is a schematic illustration of a repeating unit that may be usedin the microchannel processing unit illustrated in FIG. 3. The repeatingunit comprises a process microchannel and a staged addition channel. Anapertured section is positioned between the process microchannel andstaged addition channel. Heat exchange channels are positioned adjacentto the process microchannel. The process microchannel contains areaction zone and a mixing zone. The mixing zone is upstream of thereaction zone. The process microchannel includes surface features forapplying shear stress to the non-Newtonian fluid. The surface featuresare positioned on or in one of the interior walls of the processmicrochannel along the length of the process microchannel. A catalyst ispositioned in the reaction zone. The catalyst illustrated in FIG. 23 isin the form of a bed of particulate solids. However, the catalyst mayhave any of the forms discussed in the specification. A feed streamflows in the process microchannel. A staged addition stream flows fromthe staged addition channel through the apertured section into theprocess microchannel where it contacts the feed stream in the mixingzone to form a reactant mixture. The reactant mixture flows in thereaction zone, and reacts to form product.

FIG. 24 is a schematic illustration of a repeating unit that is the sameas the repeating unit illustrated in FIG. 23 except that part of thestaged addition stream contacts the feed steam in the mixing zone andpart of the staged addition stream contacts the feed stream in thereaction zone.

FIG. 25 is a schematic illustration of a repeating unit that is similarto the repeating unit illustrated in FIG. 23 except that the stagedaddition stream contacts the feed stream in the reaction zone. Also, thesurface features are positioned on and/or in opposite interior walls ofthe process microchannel upstream of the catalyst.

FIG. 26 is a schematic illustration of a repeating unit that is similarto the repeating unit illustrated in FIG. 25 with the exception that therepeating unit illustrated in FIG. 26 contains two adjacent sets ofprocess microchannels, staged addition channels and apertured sections.One of these sets is adjacent to and in thermal contact with the heatexchange channels while the other set is in thermal contact with theheat exchange channels.

FIG. 27 is a scanning electron microscopic (SEM) image of a porousstainless steel substrate before being heat treated. This substrate maybe used for making an apertured section which can be used to provide forflow between a staged addition channel and an adjacent processmicrochannel.

FIG. 28 is an SEM image of the substrate illustrated in FIG. 27 afterbeing heat treated. This substrate may be used for making an aperturedsection which can be used to provide for flow between a staged additionchannel and an adjacent process microchannel.

FIG. 29 is an SEM image of a tailored porous substrate which may be usedfor making an apertured section which can be used to provide for flowbetween a staged addition channel and an adjacent process microchannel.

FIG. 30 is a schematic illustration of a plan view of an apertured sheetwhich may be used in making an apertured section. The apertured sectionmay be used to provide for flow between a staged addition channel and anadjacent process microchannel.

FIG. 31 is a schematic illustration of a plan view of an apertured sheetor plate which may be used in making an apertured section. The aperturedsection may be used to provide for flow between a staged additionchannel and an adjacent process microchannel.

FIG. 32 is a schematic illustration of a relatively thin apertured sheetoverlying a relatively thick apertured sheet or plate which may be usedin making an apertured section. The apertured section may be used toprovide for flow between a staged addition channel and an adjacentprocess microchannel.

FIG. 33 is a schematic illustration of a relatively thin apertured sheetoverlying a relatively thick apertured sheet or plate which may be usedin making an apertured section. The apertured section may be used toprovide for flow between a staged addition channel and an adjacentprocess microchannel. The relatively thin sheet has a convex portionthat projects into the process microchannel.

FIG. 34 is a schematic illustration of an alternate embodiment of anaperture that may be used an the apertured section. The aperturedsection may be used to provide for flow between a staged additionchannel and an adjacent process microchannel. The aperture has a coatingpartially filling it and overlying its sidewalls.

FIG. 35 is a schematic illustration of the reaction zone of a processmicrochannel that may be used with the inventive process, the reactionzone comprising a catalyst having a packed bed configuration.

FIG. 36 is a schematic illustration of the reaction zone of a processmicrochannel that may be used with the inventive process, the reactionzone comprising a catalyst having a flow-by configuration.

FIG. 37 is a schematic illustration of the reaction zone of a processmicrochannel that may be used with the inventive process, the reactionzone comprising a catalyst having a flow-through configuration.

FIG. 38 is a schematic illustration of a process microchannel that maybe used in the inventive process, the process microchannel containing afin assembly comprising a plurality of fins, a catalyst being supportedby the fins.

FIG. 39 is a schematic illustration of an alternate embodiment of theprocess microchannel and fin assembly illustrated in FIG. 38.

FIG. 40 is a schematic illustration of an another alternate embodimentof the process microchannel and fin assembly illustrated in FIG. 38.

FIG. 41 is a schematic illustration of a microgrooved support strip thatmay be used to support a catalyst for use with the inventive process,the support strip comprising a top surface, a bottom surface, a frontedge, back edge and side edges. The microgrooves are formed in the topsurface. The microgrooves may penetrate part way or all the way throughthe support strip. Penetration of the microgrooves all the way throughthe support strip may permit fluid to flow through the microgrooves inthe direction from the top surface to the bottom surface, or vice versa.

FIG. 42( a) is a schematic illustration of a process microchannel thatmay be used in the microchannel processing unit illustrated in FIG. 3.The process microchannel contains a microgrooved support strip asillustrated in FIG. 41, the microgrooved support strip being adapted forsupporting a catalyst. FIG. 42( b) is a cross-sectional view of theprocess microchannel illustrated in FIG. 42( a) taken along line (b)-(b)in FIG. 42( a).

FIG. 43 is a schematic illustration of a process microchannel that maybe used in the microchannel processing unit illustrated in FIG. 3. Theprocess microchannel is similar to the process microchannel illustratedin FIG. 42( a) with the exception that the process microchannelillustrated in FIG. 43( a) contains opposite interior walls and acatalyst supporting microgrooved support strip positioned on each of theopposite interior walls. FIG. 43( b) is a cross-sectional view of theprocess microchannel illustrated in FIG. 43( a) taken along line (b)-(b)of FIG. 43( a).

FIG. 44 is a schematic illustration showing a plurality of microgroovedsupport strips positioned side by side forming a composite supportstructure, the front and back edges of each of the microgrooved supportstrips being open sufficiently to permit fluid to flow through suchedges. The microgrooves in each of the support strips project throughthe support strips sufficiently to permit fluid to flow through thesupport strips from one support strip to another. The composite supportstructure may be used in the reaction zones of the process microchannelsdescribed herein.

FIG. 45 is a schematic illustration of an exploded view of the compositesupport structure illustrated in FIG. 44. The support structureillustrated in FIG. 45 comprises four (4) first microgrooved supportstrips and four (4) second microgrooved support strips positioned sideby side in alternating sequence. The microgrooves in each of the supportstrips project through the support strips sufficiently to permit fluidto flow through the support strips from one support strip to another.The first microgrooved support strips employ microgrooves that formangles with the center axis of the support strips that are orientedtoward the front edges and first side edges of the support strips andare more than about 0° and less than 90°, for example, in the range fromabout 60° to about 80°. The second microgrooved support strips employmicrogrooves that form angles with the center axis of the support stripsthat are oriented toward the front edges and first side edges of thesupport strips and are more than 90° and less than about 180°, forexample, in the range from about 100° to about 120°.

FIGS. 46 and 47 are schematic illustrations of surface features that maybe used in the microchannels used with the inventive process.

FIG. 48 is a schematic illustration of a shim which has a front or firstsurface and a back or second surface, and grooves or microgrooves formedin each surface. The grooves or microgrooves in the front or firstsurface intersect the grooves or microgrooves in the back or secondsurface with the result being the formation of a plurality of voids,through holes or openings in the shim. The voids, through holes oropenings may be referred to as surface features.

FIG. 49 is a schematic illustration of an exploded view of a compositestructure comprising a plurality of the shims illustrated in FIG. 48.

FIGS. 50 and 51 are schematic illustrations of a pressurizable vesselthat may be used for housing microchannel processing units provided forin accordance with the invention.

FIG. 52 is a plot of viscosity as a function of shear rate for ashear-thinning fluid.

FIG. 53 is a schematic illustration of the experimental set-up used inthe test discussed below for predicting pressure drop.

FIG. 54 is a plot showing calibration curves for pressure transducersused in the test discussed below for predicting pressure drop.

FIG. 55 is a plot showing viscosity as a function of shear rate fornon-Newtonian fluids measured using a Brookfield viscometer.

FIG. 56 is a plot showing a comparison of experimental and predictedpressure drops for de-ionized water, the de-ionized water being aNewtonian fluid.

FIG. 57 is a plot showing a comparison of experimental pressure dropwith pressure drop predicted using Brookfield viscometer information fora low viscosity non-Newtonian fluid.

FIG. 58 is a plot showing a comparison of experimental pressure dropwith pressure drop predicted using Brookfield viscometer information fora medium viscosity non-Newtonian fluid.

FIG. 59 is a plot showing a comparison of experimental pressure dropwith pressure drop predicted using Brookfield viscometer information fora high viscosity non-Newtonian fluid.

FIG. 60 is a plot showing a comparison of experimental pressure drop andprediction with new k and n values for a low viscosity fluid.

FIG. 61 is a plot showing theorized behavior of viscosity-shear raterelationship of a power law fluid in a microchannel.

FIGS. 62 and 65-67 are schematic illustrations of microchannelprocessing units which may be used in accordance with the inventiveprocess.

FIG. 63 is a schematic illustration of a pair of shims and an orificeplate which may be used for making a repeating unit that can be used informing the microchannel processing unit illustrated in FIG. 62.

FIG. 64 is a schematic illustration of flow distribution features whichmay be used with the inventive process.

FIG. 68 is a schematic illustration of a process microchannel which hastwo process zones.

FIG. 69 is a schematic illustration of a process microchannel which hasa plurality of process zones.

DETAILED DESCRIPTION

All ranges and ratio limits disclosed in the specification may becombined. It is to be understood that unless specifically statedotherwise, references to “a,” “an,” and/or “the” may include one or morethan one and that reference to an item in the singular may also includethe item in the plural.

The term “microchannel” may refer to a channel having at least oneinternal dimension of height or width of up to about 10 millimeters(mm), and in one embodiment up to about 5 mm, and in one embodiment upto about 2 mm, and in one embodiment up to about 1 mm. The microchannelmay comprise at least one inlet and at least one outlet wherein the atleast one inlet is distinct from the at least one outlet. Themicrochannel may not be merely an orifice. The microchannel may not bemerely a channel through a zeolite or a mesoporous material. An exampleof a microchannel that may be used with the inventive process isillustrated in FIG. 1. Referring to FIG. 1, the illustrated microchannelhas a height (h), width (w) and length (l), or in the oppositedirection. Fluid may flow through the microchannel in the directionindicated by the arrows. Both the height (h) and width (w) areperpendicular to the bulk flow direction of fluid in the microchannel.The height may be referred to as a gap. The height (h) or width (w) ofthe microchannel may be in the range of about 0.05 to about 10 mm, andin one embodiment from about 0.05 to about 5 mm, and in one embodimentfrom about 0.05 to about 2 mm, and in one embodiment from about 0.05 toabout 1.5 mm, and in one embodiment from about 0.05 to about 1 mm, andin one embodiment from about 0.05 to about 0.75 mm, and in oneembodiment from about 0.05 to about 0.5 mm. The other dimension ofheight (h) or width (w) may be of any dimension, for example, up toabout 3 meters, and in one embodiment about 0.01 to about 3 meters, andin one embodiment about 0.1 to about 3 meters. The length (l) of themicrochannel may be of any dimension, for example, up to about 10meters, and in one embodiment from about 0.1 to about 10 meters, and inone embodiment from about 0.2 to about 10 meters, and in one embodimentfrom about 0.2 to about 6 meters, and in one embodiment from 0.2 toabout 3 meters. Although the microchannel illustrated in FIG. 1 has across section that is rectangular, it is to be understood that themicrochannel may have a cross section having any shape, for example, asquare, circle, semi-circle, trapezoid, etc. The shape and/or size ofthe cross section of the microchannel may vary over its length. Forexample, the height or width may taper from a relatively large dimensionto a relatively small dimension, or vice versa, over the length of themicrochannel. This is illustrated in FIG. 2.

The microchannel illustrated in FIG. 2 may be an alternate embodiment ofthe microchannel illustrated in FIG. 1. The microchannel illustrated inFIG. 2 has a cross-sectional area that varies from a maximum to aminimum. The minimum cross-sectional area may be at the outlet to themicrochannel and the maximum cross-sectional area may be at the inlet.This microchannel may be referred to as having a “narrowingcross-section.” This microchannel may be referred to as a microchannelwith a “converging cross-sectional area.” The microchannel illustratedin FIG. 2 may be referred to as a trapezoid microchannel. Themicrochannel has two dimensions of height, one being a minimum dimension(h¹) and the other being a maximum dimension (h²). The height increasesgradually from h¹ to h². Alternatively, the microchannel may have across-section in the shape of a circle, oval, triangle, etc. Themicrochannel has at least one dimension of height (h¹) that may be inthe range of about 0.05 to about 10 mm, and in one embodiment from about0.05 to about 5 mm, and in one embodiment from about 0.05 to about 2 mm,and in one embodiment from about 0.05 to about 1.5 mm, and in oneembodiment from about 0.05 to about 1 mm, and in one embodiment fromabout 0.05 to about 0.75 mm, and in one embodiment from about 0.05 toabout 0.5 mm. The width (w) may be of any dimension, for example, up toabout 3 meters, and in one embodiment about 0.01 to about 3 meters, andin one embodiment about 0.1 to about 3 meters. The length (l) may be ofany dimension, for example, up to about 10 meters, and in one embodimentfrom about 0.1 to about 10 meters, and in one embodiment from about 0.2to about 6 meters. The maximum cross-sectional may be at least abouttwo-times (2×) the minimum cross-sectional area, and in one embodimentat least about 5-times (5×), and in one embodiment at least about20-times (20×) the minimum cross-sectional area. The linear velocity (orlocal contact time between reactants and catalyst) of fluid flowing inthis microchannel may be increased as the fluid flows along the linearflow path in the microchannel in the direction indicated in FIG. 2. Anon-Newtonian fluid flowing in this microchannel in the directionindicated by the arrows may undergo increased shear resulting in areduction in viscosity. WO 03/099429 A1 is incorporated herein byreference for its disclosure of microchannels with varyingcross-sectional areas.

The term “unit operation” may refer to a process and/or apparatuswherein a chemical reaction, chemical separation (including absorption,adsorption, distillation, extraction), condensation, vaporization,distillation, heating, cooling, compression, expansion, phaseseparation, mixing, or a combination of two or more thereof, isconducted.

The term “microchannel processing unit” may refer to an apparatuscomprising at least one process microchannel wherein a non-Newtonianfluid is processed. The processing of the non-Newtonian fluid maycomprise conducting one or more unit operations. This may compriseheating the fluid, cooling the fluid, forming the fluid by mixing two ormore fluids (which may or may not be non-Newtonian fluids), contactingthe fluid with another fluid (which may or may not be a non-Newtonianfluid), conducting a reaction using one or more non-Newtonian fluids asa reactant, forming a non-Newtonian fluid by reacting one or more fluids(which may or may not be non-Newtonian fluids), separating one or morecomponents of the non-Newtonian fluid from the non-Newtonian fluid, or acombination of two or more of the foregoing. The microchannel processingunit may comprise a plurality of the process microchannels that may beoperated in parallel, a header or manifold assembly for providing forthe flow of fluid into the process microchannels, and a footer ormanifold assembly providing for the flow of fluid out of the processmicrochannels. The microchannel processing unit may comprise one or morestaged addition channels, for example staged addition microchannels,positioned adjacent to one or more of the process microchannels. Themicrochannel processing unit may comprise one or more heat exchangechannels, for example heat exchange microchannels, adjacent to and/or inthermal contact with the process microchannels for cooling and/orheating the contents of the process microchannels.

The term “process microchannel” may refer to a microchannel wherein aprocess is conducted. The process may relate to any of the unitoperations disclosed above.

The term “process zone” may refer to a section within a processmicrochannel wherein one or more unit operations are conducted.

The term “microchannel reactor” may refer to an apparatus comprising oneor more process microchannels for conducting a reaction. Themicrochannel reactor may comprise a plurality of the processmicrochannels that may be operated in parallel, a header or manifoldassembly for providing for the flow of fluid into the processmicrochannels, and a footer or manifold assembly providing for the flowof fluid out of the process microchannels. The microchannel reactor maycomprise one or more staged addition channels, for example stagedaddition microchannels, positioned adjacent to one or more of theprocess microchannels. The microchannel reactor may comprise one or moreheat exchange channels, for example heat exchange microchannels,adjacent to and/or in thermal contact with the process microchannels forcooling and/or heating the contents of the process microchannels.

The term “structured wall” or “SW” may refer to an interior channelwall, for example, a microchannel wall, with one or more strips or shimspositioned or mounted on its surface. The strips or shims may containone or more void spaces, openings or through holes. See, for example,FIGS. 48-49. These may be referred to as surface features. Two or morelayers of the strips or shims may be stacked one above another orpositioned side by side to provide a porous structure positioned ormounted on the channel wall. A catalyst may be supported by thestructured wall. An open bulk flow region or gap may be positioned inthe process microchannel adjacent the structured wall.

The term “structured wall reactor” may refer to a microchannel reactorcomprising at least one process microchannel wherein the processmicrochannel contains one or more structured walls. A catalyst may besupported by the one or more structured walls. An open bulk flow regionor gap may be positioned in the process microchannel adjacent thestructured wall.

The term “volume” with respect to volume within a process microchannelmay include all volume in the process microchannel a process fluid mayflow through or flow by. This volume may include the volume withinmicrogrooves of a microgrooved support that may be positioned in theprocess microchannel and adapted for the flow of fluid in a flow-throughmanner or in a flow-by manner. This volume may include volume withinsurface features that may be positioned in the process microchannel andadapted for the flow of fluid in a flow-through manner or in a flow-bymanner.

The term “shim” may refer to a planar or substantially planar sheet orplate. The thickness of the shim may be the smallest dimension of theshim and may be up to about 2 mm, and in one embodiment in the rangefrom about 0.05 to about 2 mm, and in one embodiment in the range ofabout 0.05 to about 1 mm, and in one embodiment in the range from about0.05 to about 0.5 mm. The shim may have any length and width.

The term “surface feature” may refer to a depression in a microchannelwall and/or a projection from a microchannel wall that modifies flowand/or mixing within the microchannel. The surface features may be inthe form of circles, spheres, frustrums, oblongs, squares, rectangles,angled rectangles, checks, chevrons, vanes, air foils, wavy shapes, andthe like. The surface features may contain subfeatures where the majorwalls of the surface features further contain smaller surface featuresthat may take the form of notches, waves, indents, holes, burrs, checks,scallops, and the like. The surface features may have a depth, a width,and for non-circular surface features a length. Examples are illustratedin FIGS. 46-47. The surface features may be formed on or in one or moreof the interior walls of the process microchannels used in accordancewith the invention. The surface features may be formed on or in one ormore of the interior walls of the heat exchange channels employedherein. The surface features may be referred to as passive surfacefeatures or passive mixing features. The surface features may be used todisrupt laminar flow streamlines and create advective flow at an angleto the bulk flow direction. This may enhance contact between fluidcomponents or between fluid components and catalyst. The surfacefeatures may comprise voids and/or protrusions formed in a structuredwall, see, for example, FIGS. 48-49.

The term “microgroove” may refer to a groove in a substrate having adepth of up to about 1000 microns, and in one embodiment in the rangefrom about 1 to about 1000 microns, and in one embodiment in the rangefrom about 1 to about 500 microns, and in one embodiment from about 1 toabout 100 microns. The microgrooves may penetrate all the way throughthe substrate over part or all of the length of the microgrooves. Themicrogrooves may penetrate only partially through the substrate. Thedepth of the microgrooves may be measured at the deepest point ofpenetration into the substrate. The microgrooves may have a width up toabout 1000 microns, and in one embodiment in the range from about 0.1 toabout 1000 microns, and in one embodiment in the range from about 1 toabout 500 microns. The width may be the width measured at the widestpoint of the microgroove. The microgroove may have any length, forexample, up to about 100 cm, and in one embodiment from about 0.1 toabout 100 cm, and in one embodiment from about 0.1 to about 10 cm. Themicrogroove may have a cross section of any shape. Examples includesquare, rectangle, vee, semi-circle, dovetail, trapezoid, and the like.The shape and/or size of the cross section of the microgroove may varyover the length of the microgroove.

The term “adjacent” when referring to the position of one channelrelative to the position of another channel may mean directly adjacentsuch that a wall separates the two channels. This wall may vary inthickness. However, “adjacent” channels may not be separated by anintervening channel that would interfere with heat transfer between thechannels.

The term “thermal contact” may refer to two bodies, for examplechannels, that are not necessarily in contact with each other oradjacent to each other but still may exchange heat with each other.Thus, for example, one body in thermal contact with another body mayheat or cool the other body.

The term “bulk flow region” may refer to open areas within a processmicrochannel. A contiguous bulk flow region may allow rapid fluid flowthrough a process microchannel without significant pressure drops. Inone embodiment there may be laminar flow in the bulk flow region. A bulkflow region may comprise at least about 5%, and in one embodiment fromabout 30 to about 80% of the internal volume of a process microchannelor the cross-sectional area of the process microchannel.

The term “bulk flow direction” may refer to the vector through whichfluid may travel in an open path in a channel.

The term “residence time,” which may also be referred to as the “averageresidence time,” may be the internal volume of a channel occupied by afluid flowing through the channel divided by the average volumetricflowrate for the fluid flowing through the channel at the temperatureand pressure being used.

The terms “upstream” and “downstream” may refer to positions within achannel (e.g., a process microchannel) that is relative to the directionof flow of a fluid stream in the channel. For example, a position withinthe channel not yet reached by a portion of a fluid stream flowingtoward that position would be downstream of that portion of the fluidstream. A position within the channel already passed by a portion of afluid stream flowing away from that position would be upstream of thatportion of the fluid stream. The terms “upstream” and “downstream” donot necessarily refer to a vertical position since the channels usedherein may be oriented horizontally, vertically or at an inclined angle.

The terms “standard cubic feet” or “standard cubic meters” may refer tovolumes measured at a temperature of 20° C. and atmospheric pressure.

The term “normal liters” may refer to volumes measured at a temperatureof 20° C. and atmospheric pressure.

The term “gauge pressure” may refer to absolute pressure, lessatmospheric pressure. For example, a gauge pressure of zero atmospherescorresponds to atmospheric pressure. However, throughout the text and inthe appended claims, unless otherwise indicated, all pressures areabsolute pressures.

The term “cycle” may refer to a single pass of reactants through theprocess microchannels.

The term “ml (milliliter) per gram of catalyst per hour” may refer to avolume (ml) of product produced per gram of catalyst per hour whereinthe gram of catalyst refers to catalytic material in the catalyst butnot any support that may be present.

The term “yield” may refer to moles of reactant converted to a specificproduct divided by the number of moles of reactant converted. The yieldmay be calculated by multiplying the conversion of the reactant by theselectivity to the product in question.

The term “superficial velocity” for the velocity of a fluid flowing in achannel may refer to the volumetric flow rate at standard pressure andtemperature divided by the open cross sectional area of the channel.

The term “immiscible” may refer to one liquid not being soluble inanother liquid or only being soluble to the extent of up to about 1milliliter per liter at 25° C.

The term “water insoluble” may refer to a material that is insoluble inwater at 25° C., or soluble in water at 25° C. up to a concentration ofabout 0.1 gram per liter.

The term “fluid” may refer to a gas, a liquid, a gas or a liquidcontaining dispersed solids, a gas containing liquid droplets, a liquidcontaining gas bubbles, a gas containing liquid droplets and dispersedsolids, or a liquid containing gas bubbles and dispersed solids.

The term “multiphase mixture” may refer to a composition containing twoor more phases. The multiphase mixture may comprise a continuous liquidphase with one or more discontinuous liquid, gas and/or solid phases(eg., solid particulates) dispersed in the continuous liquid phase. Themultiphase mixture may be an emulsion.

The term “emulsion” may refer to a composition containing a continuousliquid phase and one or more discontinuous liquid phases dispersed inthe continuous liquid phase. The emulsion may include one or more gasand/or solid phases dispersed in one or more of the liquid phases.

The term “heat source” may refer to a substance or device that gives offheat and may be used to heat another substance or device. The heatsource may be in the form of a heat exchange channel having a heatexchange fluid in it that transfers heat to another substance or device;the another substance or device being, for example, a channel that isadjacent to or in thermal contact with the heat exchange channel. Theheat exchange fluid may be in the heat exchange channel and/or it mayflow through the heat exchange channel. The heat source may be in theform of a heating element, for example, an electric heating element or aresistance heater.

The term “heat sink” may refer to a substance or device that absorbsheat and may be used to cool another substance or device. The heat sinkmay be in the form of a heat exchange channel having a heat exchangefluid in it that receives heat transferred from another substance ordevice; the another substance or device being, for example, a channelthat is adjacent to or in thermal contact with the heat exchangechannel. The heat exchange fluid may be in the heat exchange channeland/or it may flow through the heat exchange channel. The heat sink maybe in the form of a cooling element, for example, a non-fluid coolingelement.

The term “heat source and/or heat sink” may refer to a substance or adevice that may give off heat or absorb heat. The heat source and/orheat sink may be in the form of a heat exchange channel having a heatexchange fluid in it that transfers heat to another substance or deviceadjacent to or in thermal contact with the heat exchange channel whenthe another substance or device is to be heated, or receives heattransferred from the another substance or device adjacent to or inthermal contact with the heat exchange channel when the anothersubstance or device is to be cooled. The heat exchange channelfunctioning as a heat source and/or heat sink may function as a heatingchannel at times and a cooling channel at other times. A part or partsof the heat exchange channel may function as a heating channel whileanother part or parts of the heat exchange channel may function as acooling channel.

The term “heat exchange channel” may refer to a channel having a heatexchange fluid in it that may give off heat and/or absorb heat. The heatexchange channel may be a microchannel.

The term “heat transfer wall” may refer to a common wall between aprocess microchannel and an adjacent heat exchange channel where heattransfers from one channel to the other through the common wall.

The term “heat exchange fluid” may refer to a fluid that may give offheat and/or absorb heat.

The term “adjacent” when referring to the position of one channelrelative to the position of another channel may mean directly adjacentsuch that a wall separates the two channels. This wall may vary inthickness. However, “adjacent” channels may not be separated by anintervening channel that would interfere with heat transfer between thechannels.

The term “thermal contact” may refer to two bodies, for examplechannels, that are not necessarily in contact with each other oradjacent to each other but still may exchange heat with each other.Thus, for example, one body in thermal contact with another body mayheat or cool the other body.

The term “residence time,” which may also be referred to as the “averageresidence time,” may be the internal volume of a channel occupied by afluid flowing through the channel divided by the average volumetricflowrate for the fluid flowing through the channel at the temperatureand pressure being used.

The term “graded catalyst” may refer to a catalyst with one or moregradients of catalytic activity. The graded catalyst may have a varyingconcentration or surface area of a catalytically active metal. Thegraded catalyst may have a varying turnover rate of catalytically activesites. The graded catalyst may have physical properties and/or a formthat varies as a function of distance. For example, the graded catalystmay have an active metal concentration that is relatively low at theentrance to a process microchannel and increases to a higherconcentration near the exit of the process microchannel, or vice versa;or a lower concentration of catalytically active metal nearer the center(i.e., midpoint) of a process microchannel and a higher concentrationnearer a process microchannel wall, or vice versa, etc. The thermalconductivity of a graded catalyst may vary from one location to anotherwithin a process microchannel. The surface area of a graded catalyst maybe varied by varying size of catalytically active metal sites on aconstant surface area support, or by varying the surface area of thesupport such as by varying support type or particle size. A gradedcatalyst may have a porous support where the surface area to volumeratio of the support is higher or lower in different parts of theprocess microchannel followed by the application of the same catalystcoating everywhere. A combination of two or more of the precedingembodiments may be used. The graded catalyst may have a single catalyticcomponent or multiple catalytic components (for example, a bimetallic ortrimetallic catalyst). The graded catalyst may change its propertiesand/or composition gradually as a function of distance from one locationto another within a process microchannel. The graded catalyst maycomprise rimmed particles that have “eggshell” distributions ofcatalytically active metal within each particle. The graded catalyst maybe graded in the axial direction along the length of a processmicrochannel or in the lateral direction. The graded catalyst may havedifferent catalyst compositions, different loadings and/or numbers ofactive catalytic sites that may vary from one position to anotherposition within a process microchannel. The number of catalyticallyactive sites may be changed by altering the porosity of the catalyststructure. This may be accomplished using a washcoating process thatdeposits varying amounts of catalytic material. An example may be theuse of different porous catalyst thicknesses along the processmicrochannel length, whereby a thicker porous structure may be leftwhere more activity is required. A change in porosity for a fixed orvariable porous catalyst thickness may also be used. A first pore sizemay be used adjacent to an open area or gap for flow and at least onesecond pore size may be used adjacent to the process microchannel wall.

The term “hydrocarbon” may refer to purely hydrocarbon compounds; thatis, aliphatic compounds, (e.g., alkane or alkylene), alicyclic compounds(e.g., cycloalkane, cycloalkylene), aromatic compounds, aliphatic- andalicyclic-substituted aromatic compounds, aromatic-substituted aliphaticcompounds, aromatic-substituted alicyclic compounds, and the like.Examples may include methane, ethane, ethylene, propane, propylene,cyclohexane, ethyl cyclohexane, toluene, the xylenes, ethyl benzene,styrene, etc. The term “hydrocarbon” may refer to substitutedhydrocarbon compounds; that is, hydrocarbon compounds containingnon-hydrocarbon substituents. Examples of the non-hydrocarbonsubstituents may include hydroxyl, acyl, nitro, etc. The term“hydrocarbon” may refer to hetero substituted hydrocarbon compounds;that is, hydrocarbon compounds which contain atoms other than carbon ina chain or ring otherwise comprising carbon atoms. Examples of heteroatoms may include, for example, nitrogen, oxygen and sulfur. In oneembodiment, no more than about three, and in one embodiment no more thanabout one, substituents or hetero atoms may be present for each 10carbon atoms in the hydrocarbon compound.

The term “mm” may refer to millimeter. The term “nm” may refer tonanometer. The term “ms” may refer to millisecond. The term “μm” mayrefer to micron or micrometer. The terms “micron” and “micrometer” havethe same meaning and may be used interchangeably.

The non-Newtonian fluid treated and/or formed in the inventive processmay comprise any fluid polymer or polymer composition (e.g., polymersolution) that exhibits non-Newtonian properties. The non-Newtonianfluid may comprise one or more polymers or a polymer solution. Thenon-Newtonian fluid may comprise one or more molten polymers. Thepolymer may be combined with an aqueous or an organic solvent ordispersing medium. The non-Newtonian fluid may comprise a multiphasemixture or an emulsion which exhibits non-Newtonian properties. Themultiphase mixture or emulsion may comprise one or more polymers. Thesolutions, multiphase mixtures and/or emulsions may comprise aqueouscompositions.

The polymer may comprise one or more homopolymers, copolymers,terpolymers, and the like. The polymer may comprise repeating unitsderived from one or more polymerizable monomers including olefins (eg.,ethylene, propylene, isobutylene, and the like), cyclic olefins, dienes(eg., butadiene, isoprene, chloroprene), ethers, esters, amides,carbonates, acetates, acrylics, alkylacrylics, acrylates, alkylacrylates(eg., methyl acrylate, methyl methacrylate), vinyl acetate, styrene,vinyls (eg., vinyl chloride), vinylidenes (eg., vinylidene chloride,vinylidene fluoride), acrylonitrite, cyanoacrylates (eg.,methylcyanoacrylate), tetrafluoroethylene, and combinations of two ormore thereof. The polymer may comprise one or more thermoplastic resins.

The polymer may comprise one or more of polyethylene, polypropylene,polystyrene, rubber modified polystyrene, styrene-butadiene copolymers,vinyl polymers and copolymers, acrylonitrile-butadiene-styrene (ABS)copolymers, polymethylmethacrylate, polycarbonate, and the like.

The polymer may comprise one or more copolymers, terpolymers, and thelike, derived from ethylene and/or propylene, and one or more functionalmonomers, for example, alkylacrylate, acrylic acid, alkylacrylic acid,vinyl acetate, and the like. Examples of these may includeethylene/vinyl acetate copolymers; ethylene/methyl acrylate copolymers;ethylene/ethylacrylate copolymers; ethylene/butyl acrylate copolymers;ethylene/methacrylic acid copolymers; ethylene/acrylic acid copolymers;ethylene/methacrylic acid copolymers containing sodium or zinc (alsoreferred to as ionomers); acid-, anhydride- or acrylate-modifiedethylene/vinyl acetate copolymers; acid- or anhydride-modifiedethylene/acrylate copolymers; anhydride-modified polyethylenes; andmixtures of two or more thereof.

The polymer may comprise one or more natural rubbers, reclaimed rubbers,synthetic rubbers, and the like. The polymer may comprise one or morepolyisoprenes, polychloroprenes, styrene butadiene rubbers, tackifiednatural or synethetic rubbers, styrene butadiene or styrene isopreneblock copolymers, random copolymers of ethylene and vinyl acetate,ethylene-vinyl-acrylic terpolymers, polyisobutylenes, poly(vinylethers), poly(acrylic) esters, and the like.

The polymer may comprise one or more homopolymers or copolymers ofacrylic acid crosslinked with one or more polyakenyl polyethers. Thesemay be available from Noveon under the tradename Carbopol.

The non-Newtonian fluid that may be treated and/or formed using theinventive process may comprise any multiphase fluid mixture thatexhibits non-Newtonian properties. The multiphase fluid mixture may bean emulsion. The multiphase fluid mixture may comprise two or moreliquids which may be immiscible relative to each other. A third liquid,which may be immiscible relative to either or both of the other liquids,may be included. Each liquid may be organic, aqueous, or a combinationthereof. For example, one liquid may comprise benzene and the otherliquid may comprise glycerol. One of the liquids may be an ionic liquid(e.g., a salt of 1-butyl-3-methylimidazolium) while another may be anorganic liquid. One of the liquids may comprise water, and anotherliquid may comprise a hydrophobic organic liquid such as an oil. Themultiphase fluid mixture may comprise a water-in-oil (w/o) oroil-in-water (o/w) emulsion. The multiphase fluid mixture may comprise adouble emulsion, for example, a water-in-oil-in-water (w/o/w) or anoil-in-water-in-oil (o/w/o) emulsions. The term “oil” may be used torefer to an organic phase of a multiphase fluid mixture although theorganic material may or may not be an oil. One of the liquids may bepresent in the multiphase fluid mixture at a concentration in the rangefrom about 0.1 to about 99.9% by weight, and in one embodiment about 1to about 99% by weight, and in one embodiment about 5 to about 95% byweight, with the other liquid making up the difference. The thirdliquid, when used, may be present in the multiphase fluid mixture at aconcentration in the range up to about 50% by weight, and in oneembodiment from about 0.1 to about 20% by weight, and in one embodimentabout 0.5 to about 10% by weight.

One or more of the liquids in the multiphase fluid mixture may compriseone or more liquid hydrocarbons. These may comprise natural oils,synthetic oils, or mixtures thereof. The natural oils may include animaloils and vegetable oils (e.g., castor oil, lard oil) as well as mineraloils. The natural oils may include oils derived from coal or shale. Theoil may be a saponifiable oil from the family of triglycerides, forexample, soybean oil, sesame seed oil, cottonseed oil, safflower oil,and the like. The oil may be a silicone oil. The oil may be an aliphaticor naphthenic hydrocarbon such as Vaseline, squalane, squalene, or oneor more dialkyl cyclohexanes, or a mixture of two or more thereof.Synthetic oils may include hydrocarbon oils such as polymerized andinterpolymerized olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers, etc.); poly(1-hexenes), poly-(1-octenes),poly(1-decenes), etc. and mixtures thereof; alkylbenzenes (e.g.,dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes,di-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers andalkylated diphenyl sulfides and the derivatives, analogs and homologsthereof and the like. Alkylene oxide polymers and interpolymers andderivatives thereof where the terminal hydroxyl groups have beenmodified by esterification, etherification, etc., are synthetic oilsthat may be used. The synthetic oil may comprise a poly-alpha-olefin ora Fischer-Tropsch synthesized hydrocarbon. The oil may comprise anormally liquid hydrocarbon fuel, for example, a distillate fuel such asmotor gasoline as defined by ASTM Specification D439, or diesel fuel orfuel oil as defined by ASTM Specification D396.

The multiphase fluid mixture may comprise one or more fatty alcohols,fatty acid esters, or mixtures thereof. The fatty alcohol may be aGuerbet alcohol. The fatty alcohol may contain from about 6 to about 22carbon atoms, and in one embodiment about 6 to about 18 carbon atoms,and in one embodiment about 8 to about 12 carbon atoms. The fatty acidester may be an ester of a linear fatty acid of about 6 to about 22carbon atoms with linear or branched fatty alcohol of about 6 to about22 carbon atoms, an ester of a branched carboxylic acid of about 6 toabout 13 carbon atoms with a linear or branched fatty alcohol of about 6to about 22 carbon atoms, or a mixture thereof. Examples includemyristyl myristate, myristyl palmitate, myristyl stearate, myristylisostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetylmyristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyloleate, cetyl behenate, cetyl erucate, stearyl myristate, stearylpalmitate, stearyl stearate, stearyl isostearate, stearyl oleate,stearyl behenate, stearyl erucate, isostearyl myristate, isostearylpalmitate, isostearyl stearate, isostearyl isostearate, isostearyloleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleylpalmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleylbehenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenylstearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenylerucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucylisostearate, erucyl oleate, erucyl behenate and erucyl erucate. Thefatty acid ester may comprise: an ester of alkyl hydroxycarboxylic acidof about 18 to about 38 carbon atoms with a linear or branched fattyalcohol of about 6 to about 22 carbon atoms (e.g., dioctyl malate); anester of a linear or branched fatty acid of about 6 to about 22 carbonatoms with a polyhydric alcohol (for example, propylene glycol, dimerdiol or trimer triol) and/or a Guerbet alcohol; a triglyceride based onone or more fatty acids of about 6 to about 18 carbon atoms; a mixtureof mono-, di- and/or triglycerides based on one or more fatty acids ofabout 6 to about 18 carbon atoms; an ester of one or more fatty alcoholsand/or Guerbet alcohols of about 6 to about 22 carbon atoms with one ormore aromatic carboxylic acids (e.g., benzoic acid); an ester of one ormore dicarboxylic acids of 2 to about 12 carbon atoms with one or morelinear or branched alcohols containing 1 to about 22 carbon atoms, orone or more polyols containing 2 to about 10 carbon atoms and 2 to about6 hydroxyl groups, or a mixture of such alcohols and polyols; an esterof one or more dicarboxylic acids of 2 to about 12 carbon atoms (e.g.,phthalic acid) with one or more alcohols of 1 to about 22 carbon atoms(e.g., butyl alcohol, hexyl alcohol); an ester of benzoic acid withlinear and/or branched alcohol of about 6 to about 22 carbon atoms; ormixture of two or more thereof.

The multiphase fluid mixture may comprise: one or more branched primaryalcohols of about 6 to about 22 carbon atoms; one or more linear and/orbranched fatty alcohol carbonates of about 6 to about 22 carbon atoms;one or more Guerbet carbonates based on one or more fatty alcohols ofabout 6 to about 22 carbon atoms; one or more dialkyl (e.g.,diethylhexyl) naphthalates wherein each alkyl group contains 1 to about12 carbon atoms; one or more linear or branched, symmetrical ornonsymmetrical dialkyl ethers containing about 6 to about 22 carbonatoms per alkyl group; one or more ring opening products of epoxidizedfatty acid esters of about 6 to about 22 carbon atoms with polyolscontaining 2 to about 10 carbon atoms and 2 to about 6 hydroxyl groups;or a mixture of two or more thereof.

The multiphase fluid mixture may comprise water in one or more phases.The water may be taken from any convenient source. The water may bedeionized or purified using osmosis or distillation.

The multiphase fluid mixture may comprise one or more emulsifiers and/orsurfactants. The emulsifiers and/or surfactants may comprise ionic ornonionic compounds having a hydrophilic lipophilic balance (HLB) in therange of zero to about 18 in Griffin's system, and in one embodimentabout 0.01 to about 18. The ionic compounds may be cationic oramphoteric compounds. Examples include those disclosed in McCutcheonsSurfactants and Detergents, 1998, North American & InternationalEdition. Pages 1-235 of the North American Edition and pages 1-199 ofthe International Edition are incorporated herein by reference for theirdisclosure of such emulsifiers. The emulsifiers and/or surfactants thatmay be used include alkanolamines (eg., triethanolamine),alkylarylsulfonates, amine oxides, poly(oxyalkylene) compounds,including block copolymers comprising alkylene oxide repeat units,carboxylated alcohol ethoxylates, ethoxylated alcohols, ethoxylatedalkyl phenols, ethoxylated amines and amides, ethoxylated fatty acids,ethoxylated fatty esters and oils, fatty esters, fatty acid amides,glycerol esters, glycol esters, sorbitan esters, imidazolinederivatives, lecithin and derivatives, lignin and derivatives,monoglycerides and derivatives, olefin sulfonates, phosphate esters andderivatives, propoxylated and ethoxylated fatty acids or alcohols oralkyl phenols, sorbitan derivatives, sucrose esters and derivatives,sulfates or alcohols or ethoxylated alcohols or fatty esters, sulfonatesof dodecyl and tridecyl benzenes or condensed naphthalenes or petroleum,sulfosuccinates and derivatives, and tridecyl and dodecyl benzenesulfonic acids. The emulsifiers and/or surfactants may comprise: one ormore polyalkylene glycols; one or more partial esters of glycerol orsorbitan and fatty acids containing about 12 to about 22 carbon atoms;or a mixture thereof. The emulsifier and/or surfactant may comprise apharmaceutically acceptable material such as lecithin. The concentrationof these emulsifiers and/or surfactants in the emulsions may range up toabout 20% by weight of the emulsion, and in one embodiment in the rangefrom about 0.01 to about 5% by weight, and in one embodiment from about0.01 to about 2% by weight. In one embodiment, the concentration may beup to about 2% by weight, and in one embodiment up to about 1% byweight, and in one embodiment up to about 0.5% by weight.

The multiphase fluid mixture may contain one or more additionalfunctional additives. These functional additives may be premixed withany of the liquids used to form the multiphase mixture or emulsion.These functional additives may include: UV protection factors (e.g.,3-benzylidene camphor and derivatives thereof, 4-aminobenzoic acidderivatives, esters of salicylic acid, derivatives of benzophenone,esters of benzalmalonic acid, triazine derivatives,2-phenylbenzimidazole-5-sulfonic acid and salts thereof, sulfonic acidderivatives of benzophenone and salts thereof, derivatives of benzoylmethane); waxes (e.g., candelilla wax, carnauba wax, Japan wax, corkwax, rice oil wax, sugar cane wax, beeswax, petrolatum, polyalkylenewaxes, polyethylene glycol waxes); consistency factors (e.g., fattyalcohols, hydroxy fatty alcohols; partial glycerides, fatty acids,hydroxy fatty acids); thickeners (e.g., polysaccharides such as xanthangum, guar-guar and carboxymethyl cellulose, polyethylene glycolmonoesters and diesters, polyacrylates, polyacrylamides, polyvinylalcohol, polyvinyl pyrrolidone); superfatting agents (e.g., lanolin,lecithin, polyol fatty acid esters, monoglycerides, fatty acidalkanolamides); stabilizers (e.g., metal salts of fatty acids, such asmagnesium, aluminum or zinc stearate or ricinoleate); polymers (e.g.,catonic polymers such as cationic cellulose derivatives, cationicstarch, copolymers of diallyl ammonium salts and acrylamides,quaternized vinyl pyrrolidone/vinyl imidazole polymers,polyethyeneimine, cationic silicone polymers, polyaminopolyamides;anionic, zwitterionic, amphoteric and nonionic polymers); siliconecompounds (e.g., dimethyl polysiloxanes; methyl phenyl polysiloxanes;cyclic silicones; amino-, fatty acid-, alcohol-, polyether-, epoxy-,fluorine-, glycoside- and/or alkyl-modified silicone compounds;simethicones; dimethicones); fats; waxes; lecithins; phospholipids;biogenic agents (e.g., tocopherol, ascorbic acid, deoxyribonucleic acid,retinol, amino acids, plant extracts, vitamin complexes); antioxidants(e.g., amino acids, imidazoles, peptides, carotinoids, carotenes,liponic acid and derivatives thereof, aurothioglucose, propylthiouracil,dilaurylthiodipropionate, sulfoximine compounds, metal chelators such asalpha-hydroxy fatty acids, alpha-hydroxy acids such as citric or lacticacid, humic acid, bile acid, EDTA, EGTA, folic acid and derivativesthereof, vitamin complexes such as vitamins A, C or E, stilbenes andderivatives thereof); deodorants; antiperspirants; antidandruff agents;swelling agents (e.g., montmorillonites, clay minerals); insectrepellents; self-tanning agents (e.g., dihydroxyacetone); tyrosineinhibitors (depigmenting agents); hydrotropes (e.g., ethanol, isopropylalcohol, and polyols such as glycerol and alkylene glycols used toimprove flow behavior); solubilizers; preservatives (e.g.,phenoxyethanol, formaldehyde solution, parabens, pentane diol, sorbicacid), perfume oils (e.g., extracts of blossoms, fruit peel, roots,woods, herbs and grasses, needles and branches, resins and balsams, andsynthetic perfumes including esters, ethers, aldehydes, ketones,alcohols and hydrocarbons); dyes; and the like. The concentration ofeach of these additives in the multiphase fluid mixture may be up toabout 20% by weight, and in one embodiment from about 0.01 to about 10%by weight, and in one embodiment about 0.01 to about 5% by weight, andin one embodiment about 0.01 to about 2% by weight, and in oneembodiment about 0.01 to about 1% by weight. The multiphase fluidmixture may contain one or more particulate solids.

The particulate solids may be organic, inorganic, or a combinationthereof. The particulate solids may comprise catalysts (e.g., combustioncatalysts such as CeO₂/BaAl₁₂O₁₉, Pt/Al₂O₃, etc., polymerizationcatalysts, and the like), pigments (e.g., TiO₂, carbon black, ironoxides, etc.), fillers (e.g., mica, silica, talcum, barium sulfate,polyethylenes, polytetrafluoroethylene, nylon powder, methylmethacrylate powder), etc. The particulate solids may comprise nanosizeparticles. The particulate solids may have a mean particle diameter inthe range of about 0.001 to about 10 microns, and in one embodimentabout 0.01 to about 1 micron. The concentration of the particulatesolids in the multiphase fluid mixture may range up to about 70% byweight, and in one embodiment from about 0.1 to about 30% by weightbased on the weight of the emulsion.

The multiphase fluid mixture may comprise one or more discontinuousphases dispersed in a continuous phase. The discontinuous phase maycomprise gas bubbles, liquid droplets and/or particulate solids having avolume-based mean diameter of up to about 200 microns, and in oneembodiment about 0.01 to about 200 microns, and in one embodiment about0.01 to about 100 microns, and in one embodiment about 0.01 to about 50microns, and in one embodiment about 0.01 to about 25 microns, and inone embodiment about 0.01 to about 10 microns, and in one embodimentabout 0.01 to about 5 microns, and in one embodiment about 0.01 to about2 microns, and in one embodiment about 0.01 to about 1 micron, and inone embodiment about 0.01 to about 0.5 micron, and in one embodimentabout 0.01 to about 0.2 micron, and in one embodiment about 0.01 toabout 0.1 micron, and in one embodiment about 0.01 to about 0.08 micron,and in one embodiment about 0.01 to about 0.05 micron, and in oneembodiment about 0.01 to about 0.03 micron.

The discontinuous phase may comprise water and the continuous phase maycomprise an organic liquid. The discontinuous phase may comprise anorganic liquid and the continuous phase may comprise water or anotherorganic liquid. The continuous phase may contain particulate solidsdispersed or suspended in the continuous phase. The discontinuous phasemay contain gas bubbles, particulate solids and/or droplets encapsulatedwithin droplets in the discontinuous phase. An advantage of theinvention is that at least in one embodiment the gas bubbles, liquiddroplets and/or particulate solids may be characterized by having arelatively narrow distribution of bubble, droplet or particulate sizes.In one embodiment, the bubble, droplet or particulate sizes in thedispersed phase may be plotted with the result being a normaldistribution curve.

“Relative span” is often referred to as “span.” It is a dimensionlessparameter calculated from volume distribution. As with volume mediandroplet size (VMD), D[v,0.1] and D[v,0.9] are diameters representing thepoints at which 10% and 90%, respectively, of the volume of liquiddispersed is in droplets of smaller diameter. The span may be defined asD[v,0.9] minus D[v,0.1] which is then divided by the VMD (D[v,0.5]). Thespan for the bubbles, droplets or particulates may be in the range fromabout 0.005 to about 10, and in one embodiment about 0.01 to about 10,and in one embodiment about 0.01 to about 5, and in one embodiment about0.01 to about 2, and in one embodiment about 0.01 to about 1, and in oneembodiment about 0.01 to about 0.5, and in one embodiment about 0.01 toabout 0.2, and in one embodiment about 0.01 to about 0.1. In oneembodiment, the inventive process may be conducted in a single processmicrochannel and the span may be in the range of from about 0.01 toabout 0.5. In one embodiment, the inventive process may be conducted ina scaled-up process employing multiple process microchannels and thespan may be in the range from about 0.01 to about 1.

In one embodiment, the volume-based diameter for the gas bubbles, liquiddroplets and/or solid particulates may be in the range from about 0.01to about 200 microns, and the span may be in the range from about 0.005to about 10. In one embodiment, the volume-based mean diameter may be inthe range from about 0.01 to about 100 microns, and the span may be inthe range from about 0.01 to about 5. In one embodiment, thevolume-based mean diameter may be in the range from about 0.01 to about50 microns, and the span may be in the range from about 0.02 to about 5.In one embodiment, the volume-based mean diameter may be in the rangefrom about 0.01 to about 10 microns, and the span may be in the rangefrom about 0.05 to about 2.5. In one embodiment, the volume-based meandiameter may be in the range from about 0.01 to about 5 microns, and thespan may be in the range from about 0.01 to about 2. In one embodiment,the volume-based mean diameter may be in the range of about 0.01 toabout 1 micron, and the span may be in the range of about 0.005 to about1.

Multiphase fluid mixtures treated and/or formed in accordance with theinventive process may provide the advantage of enabling the manufacturerto supply the multiphase fluid mixtures in concentrate form, thusenabling the end user to add additional ingredients, such as water oroil, to obtain the final fully formulated product.

The multiphase fluid mixtures treated and/or formed by the inventiveprocess may have numerous applications. These may include personal skincare products wherein reduced concentrations of emulsifiers orsurfactants are desirable (e.g., waterproof sun screen, waterproof handcreams or lotions).

The multiphase fluid mixtures treated and/or formed by the inventiveprocess may be useful as paints or coatings. These may includewater-resistant latex paints with strong weatherability characteristics.The multiphase fluid mixtures may be useful as adhesives, glues, caulks,waterproof sealants, and the like. The inclusion of an aqueous phase inthese compositions may reduce the problem of volatile organic compounds(VOC) in these products.

The inventive process may be used in various food processingapplications, particularly continuous processing operations.

The inventive process may be used in the treatment and/or production ofagricultural chemicals where the use of a dispersed phase with a narrowdistribution of droplet sizes is advantageous for spreading thechemicals on leafs, and providing enhanced waterproofing with smallerconcentrations of chemicals. The inventive process may be used in thetreatment and/or production of agricultural chemicals such as pesticideswherein it may be desired to employ a droplet size for the dispersedphase that is smaller than the wavelength of visible light.

The inventive process may be used for the treatment and/or production ofemulsified lubricants and fuels. These may include on-board fuelemulsification systems such as those that may be used for dieselengines.

The inventive process may be used in emulsion polymerization processes.For example, it may be possible to solubilize monomers in a surfactantwith a catalyst.

The inventive process may be used to make rapid setting emulsionscontaining bitumen. These emulsions may be used as surface dressings forcement or asphalt surfaces such as roads, driveways, and the like. Theseemulsions may contain from about 60 to about 70% by weight bitumen andmay be sprayed onto the surface being treated. Chippings may be spreadon top of these surface dressings and rolled to ensure proper embeddingand alignment. This may provide a water impervious surface seal and alsoan improved surface texture.

The multiphase fluid mixtures treated and/or made using the inventiveprocess may comprise silicone emulsions. These emulsions may be used fortreating fibers and other substrates to alter their water repellantproperties.

The inventive process may be used in a crystallization process, forexample, a continuous crystallization process. This process may be usedto isolate, purify and/or produce powders of a specified size. Anexample of such crystals include highly refined sugar. In emulsioncrystallization, a melt may be crystallized within droplets of theemulsion so that homogeneous nucleation may occur at a lower rate thanin a bulk melt. This process may be conducted without solvents, and thusmay provide the advantage of low capital and operating costs.

The inventive process may be used to treat and/or make liquid crystals.The liquid crystals formed in the process may help to reduce the use ofemulsifiers and/or surfactants, as the dispersed phase may be “locked”in place.

The inventive process may be used to treat and/or make wax emulsions foradhesives, liquid soaps, laundry detergents, coatings for textiles orfabrics, and the like.

The inventive process may be used in the manufacture of pharmaceuticalswherein the provision of a dispersed oil phase with a narrowdistribution of droplet sizes is advantageous. These may include oral orinjectable compositions as well as dermatological creams, lotions andophthalmics. The droplet size and distribution achieved with theinventive process may increase the efficacy of the drug and provide forreduced levels of use of the drug for required treatments. This also mayprovide the advantage of avoiding or limiting the use of non-aqueoussolvent components which tend to solubilize organic substances used inpackaging materials. The droplet size for the dispersed oil phase forthese applications may be up to about 0.5 micron in order to avoid beingeliminated by the spleen or liver, and in one embodiment in the rangefrom about 0.01 to about 0.2 micron, and in one embodiment 0.01 to about0.1 micron. The multiphase fluid mixtures treated or produced by theinventive process may function as emulsion vehicles for insoluble orpoorly soluble drugs (e.g., ibuprofen, diazepam, griseofulvin,cyclosporin, cortisone, proleukin, etoposide, paclitaxel, cytotoxin,vitamin E, alpha-tocopherol, and the like). Many of the pharmaceuticalcompounds or drugs, oils and surfactants disclosed in U.S. PatentApplication Publication No. 200310027858A1 may be used in makingpharmaceutical compositions using the inventive process; this patentpublication is incorporated herein by reference for its disclosure ofsuch compounds or drugs, oils and surfactants. An advantage of using theinventive process relates to the fact that many of the problemsassociated with using conventional high-shear mixing equipment forattempting to achieve small droplets with a narrow droplet sizedistribution while maintaining a sterile environment may be avoided.

The invention relates to a process which employs one or more processmicrochannels, wherein each process microchannel has two or more processzones, and one or more different unit operations are conducted in eachprocess zone. With each unit operation a non-Newtonian fluid is treatedand/or formed.

The unit operation may comprise a chemical reaction, chemical separation(including sorption (i.e., absorption and/or adsorption), distillation,extraction), condensation, vaporization, heating, cooling, compression,expansion, phase separation, mixing, or a combination of two or morethereof. Thus, for example, the inventive process may comprise heating anon-Newtonian fluid in a first process zone and then conducting achemical reaction with the non-Newtonian fluid in a second or subsequentprocess zone. The non-Newtonian fluid may be heated or cooled during thechemical reaction. The process may comprise mixing various ingredientsin a first process zone to form the non-Newtonian fluid and then coolingthe non-Newtonian fluid in a second or subsequent process zone.

The inventive process may be used to heat the non-Newtonian fluid, coolthe non-Newtonian fluid, form the non-Newtonian fluid by mixing two ormore fluids (which may or may not be non-Newtonian fluids), contactand/or mix the non-Newtonian fluid with one or more other fluids (whichmay or may not be a non-Newtonian fluid) and/or particulate solids,conduct a reaction using two or more fluids (which may or may not benon-Newtonian fluids) to form a non-Newtonian fluid, conduct a reactionusing as the reactant one or more non-Newtonian fluids, compress thenon-Newtonian fluid, expand the non-Newtonian fluid, condense thenon-Newtonian fluid, vaporize the non-Newtonian fluid, separate one ormore components from the non-Newtonian fluid, or a combination of two ormore of the foregoing.

The inventive process includes applying shear stress to thenon-Newtonian fluid that is sufficient to reduce the viscosity of thenon-Newtonian fluid prior to and/or during each unit operation. Prior toconducting the inventive process the non-Newtonian fluid may haveviscosity in the range from about 10⁻³ to about 10⁸ centipoise, and inone embodiment from about 10² to about 10⁵ centipoise. The viscosity maybe reduced in each process zone to a level in the range up to about 10⁵centipoise, and in one embodiment in the range from about 10⁻⁵ to about10⁵ centipoise, and in one embodiment from about 10⁻³ to about 10³centipoise, and in one embodiment from about 10⁻³ to about 10centipoise.

The shear rate in each process zone may be in excess of about 100 sec⁻¹,and in one embodiment in excess of about 250 sec⁻¹, and in oneembodiment in excess of about 500 sec⁻¹, and in one embodiment in excessof about 750 sec⁻¹, and in one embodiment in excess of about 1000 sec⁻¹,and in one embodiment in excess of about 2500 sec⁻¹, and in oneembodiment in excess of about 500 sec⁻¹, and in one embodiment in excessof about 7500 sec⁻¹, and in one embodiment in excess of about 10,000sec⁻¹, and in one embodiment in excess of about 50,000 sec⁻¹, and in oneembodiment in excess of about 100,000 sec⁻¹. The average shear rate inone process zone may differ from the average shear rate in anotherprocess zone by a factor of at least about 1.2, and in one embodiment bya factor of at least about 1.5, and in one embodiment by a factor of atleast about 2, and in one embodiment by a factor of at least about 3,and in one embodiment by a factor of at least about 4, and in oneembodiment by a factor of at least about 5, and in one embodiment by afactor of at least about 7, and in one embodiment by a factor of atleast about 10, and in one embodiment by a factor of at least about 20,and in one embodiment by a factor of at least about 30, and in oneembodiment by a factor of at least about 40, and in one embodiment by afactor of at least about 50, and in one embodiment by a factor of atleast about 75, and in one embodiment by a factor of at least about 100.

An advantage of the inventive process relates to utilizing the nature ofnon-Newtonian fluids and optimizing channel dimensions for differentunit operations in the same process microchannel. FIG. 68 shows aprocess microchannel with separate process zones: process zone 1 andprocess zone 2. A first unit operation may be conducted in process zone1 and a different unit operation may be conducted in process zone 2. Thedependence of viscosity of the non-Newtonian fluid on shear rate may beused to select microchannel dimensions to maximize the processefficiency in each process zone. Similarly, FIG. 69 shows a processmicrochannel containing a plurality or “n” process zones. The value of nmay be any number, for example from 3 to about 20, and in one embodimentfrom 3 to about 10, and in one embodiment from 3 to about 5.

The average shear rate, γ_(avg), in a process zone may be determined bythe following formula, wherein A is the wetted surface area in theprocess zone:

$\gamma_{avg} = \frac{\int_{{Wall}\text{-}{surface}}{\gamma {A}}}{\int_{{wall}\text{-}{surface}}{A}}$

The surface area A comprises the internal surface area of the processmicrochannel walls in the process zone including protrusions and/orvoids (e.g., from surface features or a structured wall) on and/or inthe process microchannel walls. The surface area, A, does not includecatalyst or sorption material surfaces.

In one embodiment, the average shear rate in one process zone may begreater by a factor of at least about 1.2, than the average shear ratein at least about 25% of the process zones in the process microchannel.In one embodiment, the average shear rate in one process zone may begreater by a factor of at least about 1.2, than the average shear ratein at least about 50% of the process zones in the process microchannel.

Referring to FIG. 3, the process may be conducted using microchannelprocessing unit 100 which includes microchannel processing unit core102, process fluid header 104, and product footer 106. The microchannelprocessing unit core 102 may contain a plurality of processmicrochannels useful for conducting two or more unit operations fortreating and/or forming a non-Newtonian fluid. The microchannelprocessing unit core 102 may optionally contain one or more stagedaddition channels adjacent to each process microchannel and/or one ormore heat exchange channels. The staged addition channels and/or heatexchange channels may be microchannels. The process microchannels, andoptionally staged addition channels and/or heat exchange channels may bestacked in layers, one above the other, or positioned side by side. Theprocess header 104 may provide a passageway for a first fluid stream toflow into the process microchannels. The first fluid may be Newtonian ornon-Newtonian. The first fluid stream may flow into the microchannelprocessing unit 100 through the header 104, as indicated by arrow 110.Optionally, a second fluid stream may flow into the microchannelprocessing unit 100 through the header 104, as indicated by arrow 112.Optionally, one or more additional fluid streams (not shown in FIG. 3)may also flow through the header 104 into the process microchannels. Thesecond fluid and/or additional fluids may be Newtonian or non-Newtonian.The fluid streams may be mixed in the header 104 and flow into theprocess microchannels, or they may flow into the microchannel processingunit core 102 and be mixed in the process microchannels. Alternatively,the fluid streams may be mixed upstream of the header 104 and then flowthrough the header 104 into the process microchannels. The productfooter 106 may provide a passageway for product to flow from the processmicrochannels. The product may be Newtonian or non-Newtonian. Theproduct flows from the microchannel processing unit core 102 through theproduct footer 106, and out of product footer 106, as indicated by arrow114. One or more of the first fluid stream, second fluid stream,additional fluid stream, fluid stream mixtures, and/or product comprisesa non-Newtonian fluid. The product may be recycled back through themicrochannel processing unit core 102 any number of times, for example,one, two, three, four times, etc. A heat exchange fluid may flow intothe microchannel processing unit core 102, as indicated by arrow 116,through heat exchange channels in the microchannel processing unit core102, and out of the microchannel processing unit core 102, as indicatedby arrow 118. The microchannel processing unit 100 may be employed inconjunction with storage vessels, pumps, manifolds, valves, flow controldevices, conduits, and the like, which are not shown in the drawings,but would be apparent to those skilled in the art.

The microchannel processing unit core 102 may comprise a plurality ofmicrochannel processing units for conducting one or more unit operationswith the non-Newtonian fluid. The microchannel processing unit core 102may contain any number of these repeating units, for example, one, two,three, four, five, six, eight, ten, hundreds, thousands, etc. Examplesof these are illustrated in FIGS. 4-26 and 42-43.

In one embodiment the process microchannel may have a convergingcross-sectional area (see, FIG. 2, 8-12 or 19-22) in at least oneprocess zone and the shear stress may be applied to the non-Newtonianfluid by flowing the non-Newtonian fluid through the convergingcross-sectional area. In one embodiment, the process microchannel maycomprise surface features (see, FIGS. 46-47) on and/or in one or moreinterior surfaces in at least one process zone, and the shear stress maybe applied to the non-Newtonian fluid by flowing the non-Newtonian fluidin contact with the surface features. In one embodiment, the processmicrochannel may comprise one or more interior structured walls (see,FIGS. 48-49) in at least one process zone, and the shear stress may beapplied to the non-Newtonian fluid by flowing the non-Newtonian fluid incontact with one or more structured walls. The voids and/or protrusionsin the structured walls may be referred to as surface features. In oneembodiment the process microchannels may comprise a coating layercontaining voids and/or protrusions on one or more interior surfaces inat least one process zone, and the shear stress may be applied to thenon-Newtonian fluid by flowing the non-Newtonian fluid in contact withthe coating layer. In one embodiment, the process microchannel maycomprise internal flow restriction devices (e.g., static mixers,monoliths, ribs, etc.) in at least one process zone and the shear stressmay be applied to the non-Newtonian fluid by flowing the non-Newtonianfluid in contact with the flow restriction devices.

Referring to FIG. 4, repeating unit 200 comprises process microchannel210 and heat exchange zone 270. The process microchannel 210 may containtwo or more process zones. Heat exchange zone 270 comprises heatexchange channels 272. A process fluid flows in the process microchannelin the direction indicated by arrows 215 and 216. Heat exchange fluidflows in heat exchange channels 272 in a direction that is cross-currentrelative to the flow in the process microchannel 210. The heat exchangechannels 272 may be used to provide a tailored heating or coolingprofile along the length of the process microchannel 210. The processmicrochannel 210 includes opposite side walls 212 and 214. Sidewall 212may be referred to as a heat transfer wall. Surface features 217 arepositioned on and/or in sidewall 212. The process fluid may comprise thefirst fluid stream, or a mixture of the first fluid stream and secondfluid stream and optionally one or more additional fluid streams. One ormore of the fluid streams and/or the fluid mixture may be anon-Newtonian fluid. The process fluid flows from the process fluidheader 104 into the process microchannel 210 as indicated by arrow 215.The flow of the fluid in the process microchannel and the contacting ofthe surface features 217 provide for the application of shear stress onthe non-Newtonian fluid that is sufficient to reduce its viscosity. Oneor more unit operations is conducted with the non-Newtonian fluid in theprocess microchannel 210. The resulting product flows out of the processmicrochannel 210 as indicated by arrow 216. The product flows from therepeating unit 200 to and through the product footer 106. Heat exchangefluid flows in heat exchange channels 272 and exchanges heat with theprocess microchannel 210. The exchange of heat between the heat exchangechannels 272 and process microchannel 210 may result in a cooling and/orheating of the process microchannel 210.

Repeating unit 200A illustrated in FIG. 5 is the same as repeating unit200 illustrated in FIG. 4 with the exception that the surface features217 are positioned on sidewall 214, rather than sidewall 212.

Repeating unit 200B illustrated in FIG. 6 is the same as repeating unit200 illustrated in FIG. 4 with the exception that the surface features217 are positioned on both sidewalls 212 and 214.

The microchannel repeating unit 200C illustrated in FIG. 7 is the sameas repeating unit 200B illustrated in FIG. 6 with the exception that therepeating unit 200C includes two process microchannels 210 and 210Arather than one process microchannel. Repeating unit 200C comprisesprocess microchannels 210 and 210A and heat exchange zone 270. Inoperation, the first fluid stream or a mixture of the first fluid streamand the second fluid stream (and optionally one or more additional fluidstreams) flows into process microchannels 210 and 210A from processfluid header 104 as indicated by arrows 215 and 215A, respectively. Oneor more of the process fluids and/or the fluid mixture may be anon-Newtonian fluid. The process fluid contacts the surface features 217and 217A as indicated above. This provides for the application of shearstress on the non-Newtonian fluid resulting in a reduction in viscosity.The process fluid flows in the process microchannels 210 and 210A. Oneor more unit operations are conducted in the process microchannels 210and 210A. The resulting product exits the process microchannels 210 and200A as indicated by arrows 216 and 216A. The product flows from theprocess microchannels 210 and 210A to and through the product footer 106and out of the microchannel processing unit 100 as indicated by arrow114. Heat exchange fluid flowing in the heat exchange channels 272exchanges heat with the process fluids in the process microchannels 210and 210A.

The repeating unit 200D illustrated in FIG. 8 is the same as therepeating unit 200 illustrated in FIG. 4 with the exception that processmicrochannel 210 in repeating unit 200D has a converging cross-sectionalarea. The cross-sectional area at the entrance of the processmicrochannel 210 near the arrow 215 is larger than the cross-sectionalarea at the outlet of the process microchannel 210 near the arrow 216.The repeating unit 200D is also different than the repeating unit 200 byvirtue of the fact that the surface features in the repeating unit 200have been excluded in the repeating unit 200D. In operation, shearstress is applied to the non-Newtonian fluid in the process microchannel210 by flowing the non-Newtonian fluid through the convergingcross-sectional area. As the fluid flows through the processmicrochannel 210, the velocity of the fluid increases. The viscosity ofthe non-Newtonian fluid decreases. The pressure drop of the fluidflowing in the process microchannel 210 decreases. One or more unitoperations are conducted in the process microchannel 210.

The repeating unit 200E illustrated in FIG. 9 is the same as therepeating unit 200D illustrated in FIG. 8 with the exception that theprocess microchannel 210 in the repeating unit 200E includes aconverging section 218 which has a converging cross-sectional area and anon-converging section 219 which has a non-converging cross-sectionalarea. Shear stress is applied to the non-Newtonian fluid by flowing thenon-Newtonian fluid in the converging section 218. This results in areduction in viscosity. During flow in the non-converging section 219,the viscosity of the non-Newtonian fluid may increase.

The repeating unit 200F illustrated in FIG. 10 is the same as therepeating unit 200D illustrated in FIG. 8 with the exception thatsurface features 217 are formed on and/or in the interior wall 214. Inthis embodiment, enhanced shear stress may be achieved by use of thecombination of the converging cross-sectional area and the surfacefeatures 217.

The repeating unit 200G illustrated in FIG. 11 is the same as therepeating unit 200F illustrated in FIG. 10 with the exception that thesurface features 217 are positioned on the interior wall 212, ratherthan the interior wall 214.

The repeating 200H illustrated in FIG. 12 is the same as the repeatingunit 200F illustrated in FIG. 10 with the exception that the surfacefeatures 217 are positioned on both interior walls 212 and 214.

Referring to FIG. 13, microchannel repeating unit 200I comprises processmicrochannel 210, staged addition channel 240, apertured section 250,and heat exchange zone 270. The process microchannel 210 includes atleast two process zones, and opposite side walls 212 and 214. Surfacefeatures 217 are positioned on sidewall 212. Sidewall 212 may also bereferred to as a heat transfer wall. Apertured section 250 is positionedin sidewall 214 which is a common wall for process microchannel 210 andstaged addition channel 240. The apertured section 250 may be referredto as a porous section or porous substrate. The apertured section 250may comprise a sheet or plate having a plurality of apertures extendingthrough it. Additional embodiments of the apertured section 240 arediscussed in detail below. The stage addition channel 240 opens toprocess microchannel 210 through apertured section 250. The stagedaddition channel 240 may be a flow-through channel with an outletopening 243 or it may be a closed end channel. The process microchannel210 has mixing zone 211, and may have non-apertured regions (not shownin the drawings) upstream and/or downstream from mixing zone 211. Themixing zone 211 is adjacent to the apertured section 250. The mixingzone 211 may have a restricted cross section to enhance mixing. Inoperation, the first fluid stream flows into process microchannel 210,as indicated by directional arrow 215, and into the mixing zone 211. Thesecond fluid stream flows into staged addition channel 240, as indicatedby arrow 242, and then flows through apertured section 250, as indicatedby arrows 244, into the mixing zone 211. In mixing zone 211, the secondfluid stream contacts and mixes with the first fluid stream to form amultiphase mixture or an emulsion. The second fluid stream may form adiscontinuous phase (e.g., gas bubbles, liquid droplets) within thefirst fluid stream. The first fluid stream may form a continuous phase.The fluids contact the surface features 217 resulting in the applicationof shear stress on the fluids. The first and/or second fluid streamand/or resulting multiphase mixture or emulsion may be non-Newtonian.The applied shear stress reduces the viscosity of the non-Newtonianfluid. The multiphase mixture or emulsion flows from the mixing zone 211out of the process microchannel 210, as indicated by arrow 216. Thefirst and/or second fluid stream may contain a homogeneous catalyst anda reaction between the first fluid stream and the second fluid streammay be conducted in the process microchannel 210. Part of the secondfluid stream may flow through the opening 243 in the staged additionchannel 240 and be recycled back to the header 104, while the remainderof the second fluid stream may flow through the apertured section 250,as discussed above.

The microchannel repeating unit 200I has a heat exchange zone 270 whichincludes heat exchange channels 272. When heating or cooling is desired,heat exchange fluid flows through the heat exchange channels 272, andheats or cools the fluids in the process microchannel 210 and stagedaddition channel 240. The degree of heating or cooling may vary over theaxial length of the process microchannel 210 and staged addition channel240. The heating or cooling may be negligible or non-existent in somesections of the process microchannel 210 and staged addition channel240, and moderate or relatively high in other sections. Alternatively,the heat exchange fluid may flow in a direction that is countercurrentor cross current relative to the flow of fluid in the processmicrochannel 210. Alternatively, the heating or cooling may be effectedusing heating or cooling mediums other than a heat exchange fluid. Forexample, heating may be effected using an electric heating element.Cooling may be effected using a non-fluid cooling element. The electricheating element and/or non-fluid cooling element may be used to form oneor more walls of the process microchannel 210 and/or staged additionchannel 240. The electric heating element and/or non-fluid coolingelement may be built into one or more walls of the process microchannel210 and/or staged addition channel 240. Multiple heating or coolingzones may be employed along the axial length of the process microchannel210. Similarly, multiple heat exchange fluids at different temperaturesmay be employed along the length of the process microchannel 210

The fluid flowing through the process microchannel 210 may undergo apressure drop as it flows from the process microchannel inlet to theprocess microchannel outlet. As a result of this pressure drop theinternal pressure within the process microchannel 210 may decreaseprogressively from a high point near the process microchannel inlet to alow point near the process microchannel outlet. In order to produce gasbubbles or liquid droplets that are relatively uniform in size, it maybe desirable to maintain a substantially constant pressure differentialacross the apertured section 250 along the axial length of the aperturedsection 250. In order to do this, the internal pressure within thestaged addition channel 240 may be reduced along its axial length tomatch the drop in internal pressure in the process microchannel 210 as aresult of the pressure drop resulting from the flow of fluid through theprocess microchannel. This may be done by providing the staged additionchannel 240 in the form of a microchannel such that the second fluidstream flowing in the staged addition channel undergoes a pressure dropsimilar to the pressure drop for the fluid flowing through the processmicrochannel 210.

In one embodiment, the apertured section 250 may comprise a plurality ofdiscrete feed introduction points rather than a continuous introductionof the second fluid stream along the axial length of the aperturedsection 250. The number of discrete feed introduction points may be anynumber, for example, one, two, three, four, five six, seven, eight, 10,20, 50, 100, etc.

The microchannel repeating unit 200J illustrated in FIG. 14 is the sameas the microchannel repeating unit 200I illustrated in FIG. 13 exceptthat the repeating unit 200J has a first repeating section 205 and asecond repeating section 205A positioned adjacent to one another. Thefirst repeating section 205 comprises first process microchannel 210,first staged addition channel 240 and first apertured section 250. Thesecond repeating section 205A comprises a second process microchannel210A, second staged addition channel 240A, and second apertured section250A. The process microchannel 210 includes surface features 217, andthe process microchannel 210A includes surface features 217A. Heatexchange channels 272 are adjacent to and in thermal contact with thefirst repeating section 205 and are remote from but in thermal contactwith the second repeating section 205A.

The microchannel repeating unit 200K illustrated in FIG. 15 comprisesprocess microchannel 210 which includes at least two process zones, oneof which includes reaction zone 220 wherein catalyst 222 is situated,and heat exchange zone 270, which includes heat exchange channels 272.The catalyst 222 illustrated in FIG. 15 is in the form of a bed ofparticulate solids. However, any of the catalyst forms discussed in thespecification may be used in the process microchannel illustrated inFIG. 15. Surface features 217 are positioned on and/or in oppositesidewalls 212 and 214 upstream of the reaction zone 220. In operation,the first fluid stream or a mixture of the first fluid stream and thesecond fluid stream, and optionally one or more additional fluidstreams, enter the reaction zone 220, as indicated by arrow 215, contactthe catalyst 222 and react to form a product. One or more of the fluidsand/or the mixture of fluids may be non-Newtonian. Shear stress isapplied to the non-Newtonian fluid by flowing the non-Newtonian fluid incontact with the surface features 217. This reduces the viscosity of thenon-Newtonian fluid. The product flows out of the reaction zone 220, asindicated by arrow 216.

The microchannel repeating 200L illustrated in FIG. 16 comprises processmicrochannel 210, which includes at least two process zones, one ofwhich includes reaction zone 220 wherein catalyst 222 is situated, andheat exchange zone 270, which includes heat exchange channels 272. Thecatalyst 222 is positioned on interior wall 214. Surface features 217are positioned on the opposite interior wall 212. The catalyst 222 maybe positioned on a support which is mounted on the interior wall 214.The catalyst may be in any of the forms discussed in the specification.In operation, the first fluid stream or a mixture of the first fluidstream and the second fluid stream, and optionally one or moreadditional fluid streams, enter the reaction zone 220, as indicated byarrow 215, contact the catalyst 222 and react to form a product. Shearstress is applied to the non-Newtonian fluid, which may be one or moreof the reactant fluid streams and/or the product, as the non-Newtonianfluid flows through the process microchannel 210 in contact with thesurface features 217. The shear stress applied to the non-Newtonianfluid reduces the viscosity of the non-Newtonian fluid.

Repeating unit 200M illustrated in FIG. 17 is the same as repeating unit200L illustrated in FIG. 16 with the exception that the repeating unit200M includes additional surface features 217 on the interior sidewall214 upstream of the catalyst 222. The additional surface features 217 inthe repeating unit 200M provide for additional shear stress andtherefore a further reduction in viscosity in the process microchannel210 upstream of the reaction zone 220.

Repeating 200N illustrated in FIG. 18 is the same as the repeating unit200M illustrated in FIG. 17 with the exception that in the repeating200N the surface features 217 downstream of the reaction zone have beeneliminated. This provides for reduced shear stress on the productflowing out of the reaction zone 220 as compared to repeating unit 200M.

Repeating 200O illustrated in FIG. 19 is similar to repeating unit 200Dillustrated in FIG. 8 with the exception that repeating 200O includesreaction zone 220 which contains catalyst 222. The catalyst 222illustrated in FIG. 19 is in the form of a bed of particulate solids.However, any of the catalyst forms discussed in the specification may beused in the reaction zone 220. The reactants and/or product may benon-Newtonian. The process microchannel 210 has a convergingcross-sectional area which applies shear stress to the non-Newtonianfluid flowing in the process microchannel. This reduces the viscosity ofthe non-Newtonian fluid. Heat exchange is provided by the heat exchangechannels 272 which are positioned in the heat exchange zone 270.

Repeating unit 200P, which is illustrated in FIG. 20, is the same asrepeating unit 200E illustrated in FIG. 9 with the exception thatrepeating 200P includes reaction zone 220, which contains catalyst 222.The catalyst 222 illustrated in FIG. 20 is in the form of a bed ofparticulate solids. However, any of the catalyst forms discussed in thespecification may be used. The process microchannel 210 includesconverging section 218 and non-converging section 219. The reaction zone220 is positioned in the non-converging section 219. The reactants whichare non-Newtonian and which may comprise the first fluid or a mixture ofthe first fluid and second fluid and optionally one or more additionalfluids, flow in the process microchannel 210 as indicated by arrow 215,contact the catalyst 222, and form a product which flows out of theprocess microchannel 210 as indicated by arrow 216. Shear stress isapplied to the non-Newtonian fluid flowing in the converging section 218and as a result the viscosity of the non-Newtonian fluid is reduced.Heat exchange may be provided between the heat exchange channels 272 inthe heat exchange zone 270 and the process microchannel 210.

The repeating unit 200Q illustrated in FIG. 21 is the same as therepeating unit 200P illustrated in FIG. 20 with the exception that thereaction zone 220 is positioned in the converging section 218 of theprocess microchannel 210 rather than in the non-converging section 219as illustrated in FIG. 20.

The repeating unit 200R illustrated in FIG. 22 is the same as therepeating unit 200P illustrated in FIG. 20 with the exception that thereaction zone 220 is positioned partly in the converging section 218 ofprocess microchannel 210 and partly in the non-converging section 219 ofprocess microchannel 210.

Microchannel repeating unit 200S is illustrated in FIG. 23. Repeatingunit 200S comprises process microchannel 210, staged addition channel240, and apertured section 250. A common side wall 214 separates processmicrochannel 210 and staged addition channel 240. The apertured section250 is positioned in common wall 214. The apertured section 250 containsa plurality of apertures for permitting the flow of the second fluidstream through the apertured section. The process microchannel 210includes two process zones, one of which is mixing zone 211, and theother is reaction zone 220. Catalyst 222 is positioned in the reactionzone 220. The mixing zone 211 is upstream from the reaction zone 220.Surface features 217 are positioned on and/or in sidewall 212 of processmicrochannel 210. Sidewall 212 may be referred to as a heat transferwall. The first fluid stream flows into process microchannel 210, asindicated by the arrow 215, and into the mixing zone 211. The secondfluid stream flows into staged addition channel 240, as indicated byarrow 242, and from the staged addition channel 240 through theapertured section 250 into mixing zone 211, as indicated by arrows 244.The direction of flow of the second fluid stream in the staged additionchannel 240, as indicated by arrow 242, is cocurrent with the directionof flow of the first fluid stream in the process microchannel 210, asindicated by arrow 215. Alternatively, the flow of second fluid streamin the staged addition channel 240 may be counter-current orcross-current relative to the flow of the first fluid stream in theprocess microchannel 210. The first fluid stream and second fluid streamcontact each other in the mixing zone 211 and form a reactant mixture.The reactant mixture flows from the mixing zone 211 into the reactionzone 220, contacts the catalyst, and reacts to form the product. Theproduct exits the process microchannel 210, as indicated by arrow 216.The first fluid stream, the reactant mixture and/or the product may benon-Newtonian. Shear stress is applied to the non-Newtonian fluid as thenon-Newtonian fluid contacts the surface features 217. The shear stressapplied to the non-Newtonian fluid reduces the viscosity of thenon-Newtonian fluid. Heat exchange channels 272 in heat exchange zone270 exchange heat with the process fluids in the staged addition channel240 and the process microchannel 210.

In an alternate embodiment of the repeating unit 200S illustrated inFIG. 23, a supplemental mixing zone may be provided in the processmicrochannel 210 between the mixing zone 211 and the reaction zone 220.

The repeating unit 200T illustrated in FIG. 24 is the same as therepeating unit 200S illustrated in FIG. 23 with the exception that partof the second fluid stream mixes with the first fluid stream in themixing zone 211, and part of the second fluid stream mixes with thefirst fluid stream in the reaction zone 220. The amount of the secondfluid stream that mixes with the first fluid stream in the mixing zone211 may be from about 1% to about 99% by volume of the second fluidstream, and in one embodiment from about 5% to about 95% by volume, andin one embodiment from about 10% to about 90% by volume, and in oneembodiment from about 20% to about 80% by volume, and in one embodimentfrom about 30% to about 70% by volume, and in one embodiment from about40% to about 60% by volume of the second fluid stream. The remainder ofthe second fluid stream mixes with the first fluid stream in thereaction zone 220.

The repeating unit 200U illustrated in FIG. 25 is the same as therepeating unit 200T illustrated in FIG. 24 with the exception that therepeating unit 200U does not contain the separate mixing zone 211. Also,in the repeating unit 200U, the sidewalls 212 and 214 of the processmicrochannel 210 have surface features 217 on and/or in the surface ofeach upstream of the reaction zone 220. With repeating unit 200U, thesecond fluid stream flows through the apertured section 250 into thereaction zone 220 where it contacts the first fluid stream and reacts inthe presence of the catalyst 222 to form the product. The product thenflows out of the process microchannel 210, as indicated by arrow 216.

The repeating unit 200V illustrated in FIG. 26 is the same as repeatingunit 200U illustrated in FIG. 25 with the exception that the repeatingunit 200V contains two adjacent sets of process microchannels, stagedaddition channels and apertured sections. One of these sets is adjacentto the heat exchange channels 272 while the other set is remote from butin thermal contact with the heat exchange channels 272.

In an alternate embodiment, the repeating unit may comprise two processmicrochannels and a single staged addition channel. In this embodimentthe repeating unit may comprise a first process microchannel, a secondprocess microchannel, and a staged addition channel positioned betweenthe first process microchannel and the second process microchannel. Eachprocess microchannel may have a wall with an apertured section. Surfacefeatures may be positioned on and/or in one or more sidewalls in eachprocess microchannel. A catalyst may be positioned in each processmicrochannel. The first fluid flows in the first process microchanneland the second process microchannel in contact with the catalyst. Thesecond fluid flows from the staged addition channel through theapertured section in the first process microchannel in contact with thecatalyst and the first fluid and through the apertured section in thesecond process microchannel in contact with the catalyst and the firstfluid to form a reaction product. Non-Newtonian fluids flow in theprocess microchannels in contact with the surface features. This reducesthe viscosity of the non-Newtonian fluids.

The microchannel processing unit core 102 including the processmicrochannels, staged addition channels, and heat exchange channels, aswell as any process headers, process footers, heat exchange headers,heat exchange footers, and the like, may be made of any material thatprovides sufficient strength, dimensional stability and heat transfercharacteristics to permit operation of the inventive process. Thesematerials may include steel; aluminum, titanium; nickel, platinum;rhodium; copper; chromium; brass; alloys of any of the foregoing metals;polymers (e.g., thermoset resins); ceramics; glass; compositescomprising one or more polymers (e.g., thermoset resins) and fiberglass;quartz; silicon; or a combination of two or more thereof.

The flow and/or mixing within the process microchannels 210, stagedaddition channels 240, and/or heat exchange channels 272 may be modifiedby the use of surface features formed on one, two or more interior wallsof such channels. The surface features may be in the form of depressionsin and/or projections from one or more of the channel walls. Thesesurface features may be oriented at angles relative to the direction offlow through the channels. The surface features may be aligned at anangle from about 1° to about 89°, and in one embodiment from about 30°to about 75°, relative to the direction of flow. The angle oforientation may be an oblique angle. The angled surface features may bealigned toward the direction of flow or against the direction of flow.The flow of fluids in contact with the surface features may force one ormore of the fluids into depressions in the surface features, while otherfluids may flow above the surface features. Flow within the surfacefeatures may conform with the surface feature and be at an angle to thedirection of the bulk flow in the channel. As fluid exits the surfacefeatures it may exert momentum in the x and y direction for an x,y,zcoordinate system wherein the bulk flow is in the z direction. This mayresult in a churning or rotation in the flow of the fluids. This patternmay be helpful for mixing a two-phase flow as the imparted velocitygradients may create fluid shear that breaks up one of the phases intosmall and well dispersed droplets.

Two or more surface feature regions within the process microchannels 210may be placed in series such that mixing of the fluids to form amultiphase mixture or emulsion may be accomplished using a first surfacefeature region, followed by at least one second surface feature regionwhere a different flow pattern may be used. The second flow pattern maybe used to separate one or more liquids or gases from the fluid mixture.In the second surface feature region, a flow pattern may be used thatcreates a centrifugal force that drives one liquid toward the interiorwalls of the process microchannels while another liquid remains in thefluid core. One pattern of surface features that may create a strongcentral vortex may comprise a pair of angled slots on the top and bottomof the process microchannel. This pattern of surface features may beused to create a central swirling flow pattern.

The apertured section 250 may comprise an interior portion that formspart of one or more of the interior walls of each process microchannel210. A surface feature sheet may overlie this interior portion of theapertured section. Surface features may be formed in and/or on thesurface feature sheet. The second fluid may flow through the aperturedsection and the surface feature sheet into the process microchannel.Part of the second fluid may be detached from the surface of the surfacefeature sheet while part may flow within the surface features of thesurface feature sheet. The surface feature sheet may contain angledsurface features that have relatively small widths or spans relative tothe overall flow length. The surface feature sheet may providemechanical support for the apertured section. The surface features mayimpart a vortical flow pattern to the fluids in the process microchanneland promote good mixing of the two phases and or promote the formationof small emulsion droplets. The vortical flow pattern may impart shearto the second liquid flowing through the apertured section and thusreduce the size of the droplets in the bulk flow path.

Examples of the surface features are illustrated in FIGS. 46-47. Thesurface features may have two or more layers stacked on top of eachother or intertwined in a three-dimensional pattern. The pattern in eachdiscrete layer may be the same or different. Flow may rotate or advectin each layer or only in one layer. Sub-layers, which may not beadjacent to the bulk flow path of the channel, may be used to createadditional surface area. The flow may rotate in the first level ofsurface features and diffuse molecularly into the second or moresublayers to promote reaction. Three-dimensional surface features may bemade via metal casting, photochemical machining, laser cutting, etching,ablation, or other processes where varying patterns may be broken intodiscrete planes as if stacked on top of one another. Three-dimensionalsurface features may be provided adjacent to the bulk flow path withinthe microchannel where the surface features have different depths,shapes, and/or locations accompanied by sub-features with patterns ofvarying depths, shapes and/or locations.

The use of surface features or fully etched plates with patterns may beadvantageous to provide structural support for thin or weak aperturedplates or sheets used to form the apertured section. In one embodiment,the apertured sheet may be made from a polymeric material that has verysmall mean pore diameters (less than 1 micron) but can not withstand ahigh pressure differential (greater than about 10 psi, or greater thanabout 50 psi, or greater than about 100 psi, or larger) that is requiredto force the second liquid through the apertured section into theprocess microchannel. The open span required for structural support maybe reduced from the cross section of the process microchannel to theopen span and run the length of the surface feature. The span of thesurface feature may be made smaller as required if the apertured sheetor plate has reduced mechanical integrity. One advantage of the surfacefeatures, is the convective flow that may occur within the surfacefeatures such that a significant shear stress may be created at the wallof the apertured section to assist with the detachment of smalldroplets.

An example of a three-dimensional surface feature structure may includerecessed chevrons at the interface adjacent the bulk flow path of themicrochannel. Beneath the chevrons there may be a series ofthree-dimensional structures that connect to the surface featuresadjacent to the bulk flow path but are made from structures of assortedshapes, depths, and/or locations. It may be further advantageous toprovide sublayer passages that do not directly fall beneath an opensurface feature that is adjacent to the bulk flow path within themicrochannel but rather connect through one or more tortuoustwo-dimensional or three-dimensional passages. This approach may beadvantageous for creating tailored residence time distributions in themicrochannels, where it may be desirable to have a wider versus morenarrow residence time distribution.

The length and width of a surface feature may be defined in the same wayas the length and width of a microchannel. The depth may be the distancewhich the surface feature sinks into or rises above the microchannelsurface. The depth of the surface features may correspond to thedirection of stacking a stacked and bonded microchannel device withsurface features formed on or in the sheet surfaces. The dimensions forthe surface features may refer the maximum dimension of a surfacefeature; for example the depth of a rounded groove may refer to themaximum depth, that is, the depth at the bottom of the groove.

The surface features may have depths that are less than about 2 mm, andin one embodiment less than about 1 mm, and in one embodiment in therange from about 0.01 to about 2 mm, and in one embodiment in the rangefrom about 0.01 to about 1 mm, and in one embodiment in the range fromabout 0.01 mm to about 0.5 mm. The width of the surface features may besufficient to nearly span the microchannel width (for example,herringbone designs), but in one embodiment (such as fill features) mayspan about 60% or less of the width of the microchannel, and in oneembodiment about 50% or less, and in one embodiment about 40% or less,and in one embodiment from about 0.1% to about 60% of the microchannelwidth, and in one embodiment from about 0.1% to about 50% of themicrochannel width, and in one embodiment from about 0.1% to about 40%of the microchannel width. The width of the surface features may be inthe range from about 0.05 mm to about 100 cm, and in one embodiment inthe range from about 0.5 mm to about 5 cm, and in one embodiment in therange from about 1 to about 2 cm.

Multiple surface features or regions of surface features may be includedwithin a microchannel, including surface features that recess atdifferent depths into one or more microchannel walls. The spacingbetween recesses may be in the range from about 0.01 mm to about 10 mm,and in one embodiment in the range from about 0.1 to about 1 mm. Thesurface features may be present throughout the entire length of amicrochannel or in portions or regions of the microchannel. The portionor region having surface features may be intermittent so as to promote adesired mixing or unit operation (for example, separation, cooling,etc.) in tailored zones. For example, a one-centimeter section of amicrochannel may have a tightly spaced array of surface features,followed by four centimeters of a flat channel without surface features,followed by a two-centimeter section of loosely spaced surface features.The term “loosely spaced surface features” may be used to refer tosurface features with a pitch or feature to feature distance that ismore than about five times the width of the surface feature.

In one embodiment, the surface features may be in one or more surfacefeature regions that extend substantially over the entire axial lengthof a channel. In one embodiment, a channel may have surface featuresextending over about 50% or less of its axial length, and in oneembodiment over about 20% or less of its axial length. In oneembodiment, the surface features may extend over about 10% to about 100%of the axial length of the channel, and in one embodiment from about 20%to about 90%, and in one embodiment from about 30% to about 80%, and inone embodiment from about 40% to about 60% of the axial length of achannel.

FIGS. 46 and 47 show a number of different patterns that may be used forsurface features. These patterns are not intended to limit theinvention, only to illustrate a number of possibilities. As with anysurface feature, the patterns may be used in different axial or lateralsections of a microchannel. The process microchannels may comprise oneor more structured walls.

These may be formed from one or more shims. One or more of the shims maycontain one or more void spaces, openings or through holes. These may bereferred to as surface features. The shims may contain grooves ormicrogrooves that are formed in one surface of the shims or in both thefront or first surface and the back or second surface of the shims. Thegrooves or microgrooves from the first surface may intersect the groovesor microgrooves from the second surface to form a plurality of voids,through holes or openings in the shim. Examples are illustrated in FIGS.48 and 49. FIG. 48 illustrates a shim 510 which has a front or firstsurface 512 and a back or second surface 514, and a plurality of groovesor microgrooves 530 formed in each surface. The grooves or microgrooves530 formed in the front surface 512 are parallel to each other and arepositioned in an array of block patterns 550 wherein in a first blockpattern 550 the grooves or microgrooves are aligned in a first orhorizontal direction and then in an adjacent second block pattern 550the grooves or microgrooves are aligned in a second or verticaldirection. The array of block patterns 550 comprises a plurality ofblock patterns 550 arranged in successive rows positioned one aboveanother, the successive rows forming a plurality of columns positionedside by side one another. The grooves or microgrooves 530 formed in theback surface 514 are also parallel to each other and are positioned inan array of block patterns 550 similar to the block patterns 550 in thefront surface 512 with the exception that where the front surface 512has grooves or microgrooves that are aligned in a first or horizontaldirection the back surface 514 has grooves or microgrooves 530 that arealigned in a second or vertical direction. Similarly, where the frontsurface 512 has grooves or microgrooves 530 that are aligned in a secondor vertical direction the back surface 514 has grooves or microgroovesthat are aligned in a first or horizontal direction. The grooves ormicrogrooves 530 in the front surface 512 and the grooves ormicrogrooves 530 in the back surface 514 partially penetrate the shim510. The penetration of the grooves or microgrooves 530 in the frontsurface and back surface is sufficient for the grooves or microgrooves530 in the front surface 512 to intersect the grooves or microgrooves530 in the back surface 514 with the result being the formation of anarray of voids, through holes or openings 552 in the shim 510 at thepoints where the grooves or microgrooves intersect. The openings 552 maybe of sufficient size to permit a fluid to flow or diffuse through theopenings 552. The number of openings may range from about 1 to about200,000 openings per cm², and in one embodiment from about 10 to about100,000 openings per cm². The openings 552 may have average dimensions(e.g., diameter) in the range from about 1 to about 2000 microns, and inone embodiment from about 10 to about 1000 microns. The block patterns550 may have the dimensions of about 0.01 by about 500 mm, and in oneembodiment about 0.5 by about 20 mm. The separation between each blockpattern 550 and the next adjacent block pattern may be in the range fromabout 0.01 to about 10 mm, and in one embodiment about 0.1 to about 1mm. In this embodiment, the pattern is alternated in an A, B, A, Bfashion. In an alternate embodiment the geometry may be varied such thatthe surface area to volume of the structure may be different along thelength of the reactor or in different zones of the reactor. By thismanner a reaction with a very high rate of heat release near the top ofthe reactor may be advantaged by the use of a structure with a highersurface area to volume near the middle or end of the reactor where thekinetics are slower and the rate of heat transfer lower. The resultingheat generation rate along the reactor length or heat flux profile alongthe reactor length may be made more even or uniform. The pattern may befurther optimized to maximize selectivity to the desired reactionproducts. The pattern may also be optimized to create a tailoredgradient within the catalyst structure, along the length of the catalyststructure, or both.

The grooves or microgrooves 530 in the front or first surface 512intersect the grooves or microgrooves in the back or second surface 514at right angles in the illustrated embodiment, however, it is to beunderstood that the angles of intersection may be of any value (e.g.,from about 30° to about 120°) and are therefore not limited to beingonly right angles.

FIG. 49 illustrates a composite structure 502 comprising a plurality ofthe shims 510 illustrated in FIG. 59 which may be stacked one aboveanother or positioned side by side. Any number of shims 510 may bestacked one above the other or positioned side by side in the compositesupport structure 502. For example, 2, 3, 4, 6, 8, 10, 20, 30, 50, 100,etc., shims 510 may be stacked one above another.

The process microchannels 210, staged addition channels 240 and/or heatexchange channels 272 may have their interior walls coated with alipophobic coating (the same coating may also provide hydrophobicproperties) to reduce surface energy. Teflon may be an example of acoating material that may exhibit both lipophobic and hydrophobictendencies. The surface of the apertured section 240 that faces theinterior of the process microchannel 210 may be coated with a lipophobiccoating to reduce droplet drag and promote the formation of smallerdroplets. The coating on the apertured section may reduce the energyrequired to detach a droplet from the surface of the apertured section.In addition, the drag exerted on the second liquid may be lower duringdroplet detachment and while flowing beyond the apertured sectiondownstream in the process microchannel. In one embodiment, a hydrophobiccoating may be applied to the apertured section to assist with thedetachment of water droplets into an oil phase. Fluids may not wetsurfaces coated with the lipophobic coating. As such, the fluids mayslip past the surface and thus negate or reduce the usual no-slipboundary condition of fluids against a wall. As the fluids slip, thelocal friction factor may decrease as a result of reduced drag and thecorresponding pressure drop may be reduced per unit length of thechannels. The local heat transfer rate may increase as a result offorced convection over a coated surface as opposed to conductive heattransfer through a stagnant film. The effect of the coating may have adifferent impact on different types of non-Newtonian fluids. For thecase of pseudoplastic (power law) fluid without yield may appearNewtonian above shear rates that are fluid dependent. The viscosity ofthe fluid may be higher when the shear rate is below a certain value. Ifthe shear rate is locally larger because of the coated wall, then thefluid may be able to shear droplets more easily, move with less energy(lower pumping requirements), and have better heat transfer propertiesthan if the coating were not used. For the case of pseudoplastic (powerlaw) fluid with yield may still have a yield stress, at the wall theyield stress may be greatly reduced with the use of the lipophobiccoating. Heat transfer and frictional properties may be enhanced if theapparent yield is low when the coating is used as compared to when thecoating is not used. The shear-related effects may be more pronouncedfor non-Newtonian fluids than for Newtonian fluids.

The microchannel processing unit core 102 may be fabricated using knowntechniques including wire electrodischarge machining, conventionalmachining, laser cutting, photochemical machining, electrochemicalmachining, molding, water jet, stamping, etching (for example, chemical,photochemical or plasma etching) and combinations thereof.

The microchannel processing unit core 102 may be constructed by forminglayers or sheets with portions removed that allow flow passage. A stackof sheets may be assembled via diffusion bonding, laser welding,diffusion brazing, and similar methods to form an integrated device. Themicrochannel processing unit core 102 may be assembled using acombination of sheets or laminae and partial sheets or strips. In thismethod, the channels or void areas may be formed by assembling strips orpartial sheets to reduce the amount of material required.

In one embodiment, subsections or modular units of the microchannelprocessing unit core 102 may be fabricated using the followingcomponents: a substrate piece with a hermetically sealed perimeter andopen top/bottom for process flow; and a heat exchange piece. Thesubstrate piece and heat exchange piece may be joined (welded, glued,soldered, etc.) to form a leak-free operating unit. The heat exchangepiece may be extruded. The substrate piece and the heat exchange piecemay be made from plastic, metal, or other materials as discussed above.

In one embodiment, the microchannel processing unit core 102 may be madeby a process that comprises laminating or diffusion bonding shims madeof any of the above-indicated materials (e.g., metal, plastic orceramic) so that each layer has a defined geometry of channels andopenings through which to convey fluids. After the individual layershave been created, the catalyst may be inserted. The layers may then bestacked in a prescribed order to build up the lamination. The layers maybe stacked side-by-side or one above the other. The completed stack maythen be diffusion bonded to prevent fluids from leaking into or out ofthe microchannel processing unit. After bonding, the device may betrimmed to its final size and prepared for attachment of pipes andmanifolds.

Feature creation methods include photochemical etching, milling,drilling, electrical discharge machining, laser cutting, and stamping. Auseful method for mass manufacturing may be stamping. In stamping, careshould be taken to minimize distortion of the material and maintaintight tolerances of channel geometries. Preventing distortion,maintaining shim alignment and ensuring that layers are stacked in theproper order are factors that should be controlled during the stackingprocess.

The stack may be bonded through a diffusion process. In this process,the stack may be subjected to elevated temperatures and pressures for aprecise time period to achieve the desired bond quality. Selection ofthese parameters may require modeling and experimental validation tofind bonding conditions that enable sufficient grain growth betweenmetal layers.

The next step, after bonding, may be to machine the device. A number ofprocesses may be used, including conventional milling with high-speedcutters, as well as highly modified electrical discharge machiningtechniques. A full-sized bonded microchannel reactor or microchannelseparator unit or sub-unit that has undergone post-bonding machiningoperations may comprise, for example, tens, hundreds or thousands ofshims.

The process microchannels 210 may have a height or width in the rangefrom about 0.05 to about 10 mm, and in one embodiment from about 0.05 toabout 5 mm, and in one embodiment from about 0.05 to about 2 mm, and inone embodiment from about 0.05 to about 1.5 mm, and in one embodimentfrom about 0.05 to about 1 mm, and in one embodiment from about 0.05 toabout 0.75 mm, and in one embodiment from about 0.05 to about 0.5 mm.The other dimension of height or width may be of any dimension, forexample, up to about 3 meters, and in one embodiment about 0.01 to about3 meters, and in one embodiment about 0.1 to about 3 meters. The lengthof the process microchannel 210 may be of any dimension, for example, upto about 10 meters, and in one embodiment from about 0.1 to about 10meters, and in one embodiment from about 0.2 to about 10 meters, and inone embodiment from about 0.2 to about 6 meters, and in one embodimentfrom 0.2 to about 3 meters. The process microchannel 210 may have across section that is rectangular, or alternatively it may have a crosssection having any shape, for example, a square, circle, semi-circle,trapezoid, etc. The shape and/or size of the cross section of theprocess microchannel 210 may vary over its length. For example, theheight or width may taper from a relatively large dimension to arelatively small dimension, or vice versa, over the length of themicrochannel.

The process microchannel 210 may have the construction illustrated inFIG. 2. The microchannel illustrated in FIG. 2 has a cross-sectionalarea that varies from a maximum to a minimum. In one embodiment, theminimum cross-sectional area may be at or near the outlet of themicrochannel and the maximum cross-sectional area may be at or near theinlet. This microchannel may be referred to as a microchannel with aconverging cross-sectional area. This microchannel may be referred to asa trapezoid microchannel. The microchannel has two dimensions of height,one being a minimum dimension (h¹) and the other being a maximumdimension (h²). The height increases gradually from h¹ to h².Alternatively, the microchannel may have a cross-section in the shape ofa circle, oval, triangle, etc. The microchannel has at least onedimension of height (h¹) that may be in the range of about 0.05 to about10 mm, and in one embodiment from about 0.05 to about 5 mm, and in oneembodiment from about 0.05 to about 2 mm, and in one embodiment fromabout 0.05 to about 1.5 mm, and in one embodiment from about 0.05 toabout 1 mm, and in one embodiment from about 0.05 to about 0.75 mm, andin one embodiment from about 0.05 to about 0.5 mm. The width (w) may beof any dimension, for example, up to about 3 meters, and in oneembodiment about 0.01 to about 3 meters, and in one embodiment about 0.1to about 3 meters. The length (l) may be of any dimension, for example,up to about 10 meters, and in one embodiment from about 0.1 to about 10meters, and in one embodiment from about 0.2 to about 6 meters. Themaximum cross-sectional area may be at least about two-times (2×) theminimum cross-sectional area, and in one embodiment at least about5-times (5×), and in one embodiment at least about 20-times (20×) theminimum cross-sectional area. The linear velocity of fluid flowing inthis microchannel may be increased as the fluid flows along the linearflow path in the microchannel. The local contact time between reactantsand catalyst may be reduced as the reactants flow along the linear pathin the microchannel.

The staged addition channels 240 and 240A may be microchannels or theymay have larger dimensions. The staged addition channels 240 and 240Amay have cross sections with any shape, for example, a square,rectangle, circle, semi-circle, etc. The staged addition channels 240and 240A may have an internal height or gap of up to about 10 mm, and inone embodiment up to about 6 mm, and in one embodiment up to about 4 mm,and in one embodiment up to about 2 mm. In one embodiment, the height orgap may be in the range of about 0.05 to about 10 mm, and in oneembodiment about 0.05 to about 6 mm, and in one embodiment about 0.05 toabout 4 mm, and in one embodiment about 0.05 to about 2 mm. The width ofstaged addition channel 240 and 240A may be of any dimension, forexample, up to about 3 meters, and in one embodiment about 0.01 to about3 meters, and in one embodiment about 0.1 to about 3 meters. The lengthof each and staged addition channel 240 and 240A may be of anydimension, for example, up to about 10 meters, and in one embodimentfrom about 0.1 to about 10 meters, and in one embodiment from about 0.2to about 10 meters, and in one embodiment from about 0.2 to about 6meters, and in one embodiment from 0.2 to about 3 meters.

The heat exchange channels 272 may be microchannels or they may havelarger dimensions. Each of the heat exchange channels 272 may have across section having any shape, for example, a square, rectangle,circle, semi-circle, etc. Each of the heat exchange channels 272 mayhave an internal height or gap of up to about 10 mm, and in oneembodiment in the range of about 0.05 to about 10 mm, and in oneembodiment from about 0.05 to about 5 mm, and in one embodiment fromabout 0.05 to about 2 mm. The width of each of these channels may be ofany dimension, for example, up to about 3 meters, and in one embodimentfrom about 0.01 to about 3 meters, and in one embodiment about 0.1 toabout 3 meters. The length of each of the heat exchange channels 272 maybe of any dimension, for example, up to about 10 meters, and in oneembodiment from about 0.1 to about 10 meters, and in one embodiment fromabout 0.2 to about 6 meters, and in one embodiment from 0.2 to about 3meters.

In one embodiment, the process microchannels, optional staged additionchannels, and heat exchange channels used in the microchannel processingunit core 102 may have rectangular cross sections and be aligned inside-by-side vertically oriented planes or horizontally oriented stackedplanes. These planes may be tilted at an inclined angle from thehorizontal. These configurations may be referred to as parallel plateconfigurations. Various combinations of two or more processmicrochannels, and optionally adjacent staged addition channels, with asingle heat exchange channel, or two or more heat exchange channels incombination with a single process microchannel, and optionally adjacentstaged addition channels, may be employed. An array of these rectangularchannels may be arranged in a modularized compact unit for scale-up.

The cross-sectioned shape and size of the process microchannels may varyalong their axial length to accommodate changing hydrodynamics withinthe channel. For example, if a reaction is conducted and one of thereactants is in excess, the fluidic properties of the reaction mixturemay change over the course of the reaction. Surface features may be usedto provide a different geometry, pattern, angle, depth, or ratio of sizerelative to the cross-section of the process microchannel along itsaxial length to accommodate these hydrodynamic changes.

The separation between adjacent process microchannels, staged additionchannels and/or heat exchange channels may be in the range from about0.05 mm to about 50 mm, and in one embodiment about 0.1 to about 10 mm,and in one embodiment about 0.2 mm to about 2 mm.

The process microchannels and the staged addition channels may be formedfrom parallel spaced sheets and/or plates, the staged addition channelsbeing adjacent to the process microchannels. The heat exchange channelsmay be formed from parallel spaced sheets and/or plates. The heatexchange channels may be adjacent to the process microchannels, thestaged addition channels, or both the process microchannels and thestaged addition channels. The process microchannels and staged additionchannels may be aligned in interleaved side-by-side planes orinterleaved planes stacked one above another.

The process microchannel and the staged addition channel may comprisecircular tubes aligned concentrically. The process microchannel may bein an annular space and the staged addition channel may be in the centerspace or an adjacent annular space. The process microchannel may be inthe center space and the staged addition channel may be in an adjacentannular space.

The reaction zone 220 in the process microchannel 210 may becharacterized by having a bulk flow path. The term “bulk flow path”refers to an open path (contiguous bulk flow region) within the processmicrochannels. A contiguous bulk flow region allows rapid fluid flowthrough the process microchannels without large pressure drops. In oneembodiment, the flow of fluid in the bulk flow region is laminar. Bulkflow regions within each process microchannel 210 may have across-sectional area in the range from about 0.05 to about 10,000 mm²,and in one embodiment from about 0.05 to about 5000 mm², and in oneembodiment from about 0.1 to about 2500 mm². The bulk flow regions maycomprise from about 5% to about 95%, and in one embodiment from about30% to about 80% of the cross-section of the process microchannels.

The apertures in the apertured section 250 and 250A may be of sufficientsize to permit the flow of the second fluid stream through the aperturedsections. The apertures may be referred to as pores. The aperturedsections 250 and 250A containing the foregoing apertures may havethicknesses in the range from about 0.01 to about 50 mm, and in oneembodiment about 0.05 to about 10 mm, and in one embodiment about 0.1 toabout 2 mm. The apertures may have average diameters in the range up toabout 250 microns, and in one embodiment up to about 100 microns, and inone embodiment up to about 50 microns, and in one embodiment in therange from about 0.001 to about 50 microns, and in one embodiment fromabout 0.05 to about 50 microns, and in one embodiment from about 0.1 toabout 50 microns. In one embodiment, the apertures may have averagediameters in the range from about 0.5 to about 10 nanometers (nm), andin one embodiment about 1 to about 10 nm, and in one embodiment about 5to about 10 nm. The number of apertures in the apertured sections may bein the range from about 1 to about 5×10⁸ apertures per squarecentimeter, and in one embodiment about 1 to about 1×10⁶ apertures persquare centimeter. The apertures may or may not be isolated from eachother. A portion or all of the apertures may be in fluid communicationwith other apertures within the apertured section. That is, a fluid mayflow from one aperture to another aperture. The ratio of the thicknessof the apertured sections 250 and 250A to the length of the aperturedsections along the flow path of the fluids flowing through the processmicrochannels 210 may be in the range from about 0.001 to about 1, andin one embodiment about 0.01 to about 1, and in one embodiment about0.03 to about 1, and in one embodiment about 0.05 to about 1, and in oneembodiment about 0.08 to about 1, and in one embodiment about 0.1 toabout 1.

The apertured sections 250 and 250A may be constructed of any materialthat provides sufficient strength and dimensional stability to permitthe operation of the inventive process. These materials include: steel(e.g., stainless steel, carbon steel, and the like); monel; inconel;aluminum; titanium; nickel; platinum; rhodium; copper; chromium; brass;alloys of any of the foregoing metals; polymers (e.g., thermosetresins); ceramics; glass; composites comprising one or more polymers(e.g., thermoset resins) and fiberglass; quartz; silicon; microporouscarbon, including carbon nanotubes or carbon molecular sieves; zeolites;or a combination of two or more thereof. The apertures may be formedusing known techniques such as laser drilling, microelectro machiningsystem (MEMS), lithography electrodeposition and molding (LIGA),electrical sparkling, photochemical machining (PCM), electrochemicalmachining (ECM), electrochemical etching, and the like. The aperturesmay be formed using techniques used for making structured plastics, suchas extrusion, or membranes, such as aligned carbon nanotube (CNT)membranes. The apertures may be formed using techniques such assintering or compressing metallic powder or particles to form tortuousinterconnected capillary channels and the techniques of membranefabrication. The apertures may be reduced in size from the size providedby any of these methods by the application of coatings over theapertures internal side walls to partially fill the apertures. Theselective coatings may also form a thin layer exterior to the porousbody that provides the smallest pore size adjacent to the continuousflow path. The smallest average pore opening may be in the range fromabout one nanometer to about several hundred microns depending upon thedesired droplet size for the emulsion. The apertures may be reduced insize by heat treating as well as by methods that form an oxide scale orcoating on the internal side walls of the apertures. These techniquesmay be used to partially occlude the apertures to reduce the size of theopenings for flow. FIGS. 27 and 28 show a comparison of SEM surfacestructures of a stainless steel porous substrate before and after heattreatment at the same magnification and the same location. FIG. 27 showsthe surface before heat treating and FIG. 28 shows the surface afterheat treating. The surface of the porous material after the heattreatment has a significantly smaller gap and opening size. The averagedistance between the openings is correspondingly increased.

The apertured sections 250 and 250A may be made from a metallic ornonmetallic porous material having interconnected channels or pores ofan average pore size in the range from about 0.01 to about 1000 microns,and in one embodiment in the range from about 0.01 to about 200 microns.These pores may function as the apertures. The porous material may bemade from powder or particulates so that the average inter-pore distanceis similar to the average pore size. The porous material may be tailoredby oxidization at a high temperature in the range from about 300° C. toabout 1000° C. for a duration of about 1 hour to about 20 days, or bycoating a thin layer of another material such as alumina by sol coatingor nickel using chemical vapor deposition over the surface and theinside of pores to block the smaller pores, decrease pore size of largerpores, and in turn increase the inter-pore distance. An SEM image of atailored substrate or apertured section is shown in FIG. 29.

The making of substrates for use as apertured sections 250 and 250A withsufficiently small micro-scale apertures or pores to provide a secondfluid stream having bubble or droplet sizes smaller than about onemicron can be problematic. One of the reasons for this lies in the factthat relatively high surface roughness occurs with untreated regularporous materials such as a metallic porous substrates made frompowder/particles by compression and/or sintering. These metallic poroussubstrates typically do not have the required pore size in the surfaceregion when a given nominal pore size is lower than a certain value.While the bulk of the porous material may have the specified nominalpore size, the surface region is often characterized by merged pores andcavities of much larger sizes. This problem can be overcome by tailoringthese substrates to provide for the desired pore size and inter-poredistance in the surface region. This may be done by removing a surfacelayer from the porous substrate and adding a smooth new surface withsmaller openings. The droplet size or bubble size of staged additionfeed stream that may be formed using these tailored substrates may bereduced without increasing the pressure drop across the substrate. Sincedirect grinding or machining of the porous surface may cause smearing ofthe surface structure and blockage of the pores, the porous structuremay be filled with a liquid filler, followed by solidification andmechanical grinding/polishing. The filler is then removed to regain theporous structure of the material. The filler may be a metal with a lowmelting point such as zinc or tin or the precursor of a polymer such asan epoxy. The liquid filling and removing steps may be assisted by theuse of a vacuum. Grinding/polishing may be effected using a grindingmachine and a grinding powder. Metal filler removal may be effected bymelting and vacuum suction, or by acid etching. Epoxies or otherpolymers may be removed by solvent dissolution or by burn-off in air.

Referring to FIGS. 30-32, the apertured sections 250 and 250A, in oneembodiment, may be constructed of a relatively thin sheet 300 containingrelatively small apertures 302, and a relatively thick sheet or plate310 containing relatively large apertures 312. The sheet 300 and sheetor plate 310 may each be referred to as orifice plates. The apertures312 may be aligned with or connected to the apertures 302. Therelatively thin sheet 300 may overlie and be bonded to the relativelythick sheet or plate 310, the relatively thin sheet 300 facing theinterior of process microchannel 210 and the relatively thick sheet 310facing the interior of the staged addition channel 250 or 250A. Therelatively thin sheet 300 may be bonded to the relatively thick sheet310 using any suitable procedure (e.g., diffusion bonding) to provide acomposite construction 320 with enhanced mechanical strength. Therelatively thin sheet 300 may have a thickness in the range from about0.001 to about 0.5 mm, and in one embodiment about 0.05 to about 0.2 mm.The relatively small apertures 302 may have any shape, for example,circular, triangular or rectangular. The relatively small apertures 302may have an average diameter in the range from about 0.05 to about 50microns, and in one embodiment about 0.05 to about 20 microns. Therelatively thick sheet or plate 310 may have a thickness in the rangefrom about 0.01 to about 5 mm, and in one embodiment about 0.1 to about2 mm. The relatively large apertures 312 may have any shape, forexample, circular, triangular or rectangular. The relatively largeapertures 312 may have an average diameter in the range from about 0.01to about 4000 microns, and in one embodiment about 1 to about 2000microns, and in one embodiment about 10 to about 1000 micron. The totalnumber of apertures 302 in sheet 300 and the total number of apertures312 in sheet or plate 310 may be in the range from about 1 to about10000 apertures per square centimeter, and in one embodiment from about1 to about 1000 apertures per square centimeter. The sheet 300 and thesheet or plate 310 may be constructed of any of the materials describedabove as being useful for constructing the apertured sections 250 and250A. The apertures 302 and 312 may be aligned or connected in such amanner that fluid flowing through the apertured sections 250 and 250Aflows initially through the apertures 312 then through the apertures302. The relatively short passageway for the fluid to flow through therelatively small apertures 302 enables the fluid to flow through theapertures 302 with a relatively low pressure drop as compared to thepressure drop that would occur if the passageway in the apertures had adepth equal to the combined depth of apertures 302 and 312.

In the embodiment illustrated in FIG. 33, the composite construction 320a has the same design as illustrated in FIG. 32 with the exception thatconvex portion 304 of the relatively thin sheet 300 covering theaperture 312 is provided. Convex portion 304 provides increased localshear force in the adjacent channel. The staged addition feed streamflows through the apertures 312 and 302 in the direction indicated byarrow 323. The directional arrows 322 in FIG. 33 show the flow of thefeed composition in the process microchannel adjacent to the aperture302. The increased local shear force leads to a smaller droplet size orgas bubble for the fluid flowing through the aperture 302.

In the embodiment illustrated in FIG. 34, a surface coating 330 isdeposited on the surface of sheet or plate 332 and on the internalsidewalls 334 of aperture 336. This coating provides a facilitated wayof reducing the diameter of the apertures. The coating material used toform coating 330 may be alumina, nickel, gold, or a polymeric material(e.g., Teflon). The coating 330 may be applied to the sheet or plate 332using known techniques including chemical vapor deposition, metalsputtering, metal plating, sintering, sol coating, and the like. Thediameter of the apertures may be controlled by controlling the thicknessof the coating 330.

The apertured sections 250 and 250A may be formed from an asymmetricporous material, for example, a porous material having multiple layersof sintered particles. The number of layers may be two, three, or more.An advantage of these multilayered substrates is that they provideenhanced durability and adhesion. Examples include sintered ceramicsthat have relatively large pores on one side and relatively small poreson the other side. The relatively small pores may have diameters in therange of about 2 to about 10 nm. The relatively small pores may bepositioned in a relatively thin layer of the multilayered substrate. Therelatively thin layer may have a thickness in the range of about 1 toabout 10 microns. The side with the relatively small pores may be placedfacing the interior of the process microchannel 210 to take advantage ofrelatively high shear forces to remove the relatively small droplets ofreactant and/or liquid catalyst as they are formed.

The apertured sections 250 and 250A may extend along at least about 5%of the axial length of the process microchannel 210, and in oneembodiment at least about 20% of the axial length of the processmicrochannel, and in one embodiment at least about 35% of the axiallength of the process microchannel, and in one embodiment at least about50% of the axial length of the process microchannel, and in oneembodiment at least about 65% of the axial length of the processmicrochannel, and in one embodiment at least about 80% of the axiallength of the process microchannel, and in one embodiment at least about95% of the axial length of the process microchannel, and in oneembodiment from about 5% to about 100% of the axial length of theprocess microchannel, and in one embodiment from about 10% to about 95%of the axial length of the process microchannel, and in one embodimentfrom about 25% to about 75% of the axial length of the processmicrochannel, and in one embodiment from about 40% to about 60% of theaxial length of the process microchannel 210.

The microchannel processing unit 100 may comprise one or more of therepeating units 200-200X illustrated in FIGS. 4-26 and 42-43. In oneembodiment, the microchannel processing unit may comprise from 1 toabout 50,000 of the repeating units, and in one embodiment from about 10to about 50,000 of the repeating units, and in one embodiment from about10 to about 30,000 repeating units, and in one embodiment from about 10to about 10,000 of the repeating units, and in one embodiment from about10 to about 5000 repeating units, and in one embodiment from about 10 toabout 2000 repeating units, and in one embodiment from about 10 to about1000 repeating units, and in one embodiment from about 10 to about 500repeating units, and in one embodiment from about 10 to about 100repeating units.

The inventive process may involve the use of non-Newtonian and/orNewtonian feed streams which may be used to form a non-Newtonianproduct. For example, when forming a non-Newtonian emulsion as theproduct, the following combinations of feed streams may be used:

Continuous Phase Dispersed Phase Case (Feed A) (Feed B) Product/emulsion1 Newtonian Newtonian Non-Newtonian 2 Newtonian Non-NewtonianNon-Newtonian 3 Non-Newtonian Newtonian Non-Newtonian 4 Non-NewtonianNon-Newtonian Non-Newtonian

Two approaches may be adopted for the design of the process fluid header104. The header 104 may comprise one or more inlet manifolds for each ofthe inlet feed streams. When the inlet feed stream is a Newtonian fluid,the inlet feed stream may flow straight through the inlet manifold intothe process microchannels without making any turns in the inlet manifoldor the inlet feed stream may make one or more turns in the inletmanifold prior to entering the process microchannels. On the other hand,when the inlet feed stream is a non-Newtonian fluid, the inlet feedstream may flow through the inlet manifold directly into the processmicrochannels without making any turns in the inlet manifold. The samemay be true with respect to the product footer 106, which may comprisean outlet manifold. When the product that is formed in the processmicrochannels is a non-Newtonian fluid, the product may flow directlythrough the footer 106 out of the microchannel processing unit 100. Thefooter 106 may comprise one or more straight through outlet manifoldswherein the fluid flows through the manifold without making any turns inthe outlet manifold. Various manifold designs which may be used in theheader 104 and footer 106 are disclosed in U.S. Patent Publication Nos.2005/0087767 A1, 2006/0275185 A1, and 2006/0289662 A1, which areincorporated herein by reference.

The flow patterns for Cases 1-4 referred to in the table above areillustrated in FIGS. 62, 66 and 67. In each of FIGS. 62, 66 and 67, amicrochannel processing unit 100 is used. These are the same as themicrochannel processing unit 100 illustrated in FIG. 3 with theexception that the headers disclosed in these figures are different.Each of these microchannel processing units comprise microchannelprocessing unit core 102, process fluid header 104 and product footer106. Case 1 is illustrated in FIG. 62. Referring to FIG. 62, both feedstreams A and B are Newtonian fluids which enter the header 104. Theheader 104 includes one or more inlet manifolds for each of the feedstreams. Each of the feed streams enter the header from a side of theheader and make one or more turns in the inlet manifolds to flow intothe process microchannels in the microchannel processing unit core 102.The product emulsion, which is non-Newtonian, flows from the processmicrochannels directly through footer 106 out of the microchannelprocessing unit 100. The product may flow through one or more outletmanifolds in the footer 106 without making turns in the outlet manifold.

For Cases 2 and 3, the flow patterns are illustrated in FIG. 66.Referring to Case 2 in FIG. 66, the feed stream A, which is Newtonian,flows into the header 104 from a side of the header. The header includesat least one inlet manifold for each feed stream. Feed stream A makes atleast one turn within the inlet manifold prior to entering the processmicrochannels. The feed stream B, which is non-Newtonian, flows directlythrough the inlet manifold in the header 104 into the processmicrochannels without making any turns in the inlet manifold. The feedstreams A and B are mixed in the process microchannels to form theproduct emulsion which flows directly through the footer 106 and out ofthe microchannel processing unit 100. The product may flow through oneor more outlet manifolds in the footer 106 without making any turns inthe outlet manifolds.

Case 3, which is also illustrated in FIG. 66, is the same as Case 2 withthe exception that the feed stream B is the Newtonian fluid which flowsinto the header 104 from a side of the header and into one or more inletmanifolds. Feed stream B makes one or more turns in the inlet manifoldsprior to entering the process microchannels. The feed stream A, which isnon-Newtonian, flows directly through one or more inlet manifolds in theheader 104 without making any turns in the inlet manifolds. The productemulsion flows directly through the footer 106 and out of themicrochannel processing unit 100. The product may flow through one ormore outlet manifolds in the footer 106 without making any turns in theoutlet manifolds.

Case 4, which is illustrated in FIG. 67, involves the use of inlet feedstreams A and B, both of which are non-Newtonian. Both feed streams flowdirectly through the inlet manifolds in the header 104 without makingany turns in the inlet manifolds. The product emulsion, which isnon-Newtonian, flows directly through the footer 106 and out of themicrochannel processing unit 104. The product may flow through one ormore outlet manifolds in the footer 106 without making any turns in theoutlet manifolds.

The microchannel device illustrated in FIG. 62 may be formed using theshims and orifice plate illustrated in FIG. 63. The shim on the leftprovides for the inlet and flow of feed stream A. The shim on the rightprovides for the inlet and flow of feed stream B. These shims may bestacked one above the other with the orifice plate illustrated in thecenter of FIG. 63 positioned between the shims. The two shims andorifice plate illustrated in FIG. 63 may comprise a single repeatingunit which may be used to form the microchannel processing unit 100.Additional repeating units similar to the foregoing may be stacked oneabove the other. Additional shims providing for heat exchange channels272 may be interleaved between the repeating units.

In order to control the distribution of feed from the inlet manifold tothe process microchannels, flow resistors and/or flow distributionfeatures may be provided in the manifold to control the distribution offlow from the inlet manifold to the process microchannels. A flowresistor may be an obstruction or an area of increased channel wallroughness that reduces the mass flow rate through the manifold. Examplesof flow resistors that may be used are disclosed in the above-mentionedU.S. Patent Publications 2005/0087767 A1 and 2006/0275185 A1.

A flow distribution feature may be a micro-dimensioned channelconnecting an inlet manifold to a process microchannel. Examples ofconnecting flow distribution features that may be used are illustratedin FIG. 64. In each of the illustrations provided in FIG. 64, amicro-dimensioned channel is shown which provides for the flow of fluidfrom the manifold to a process microchannels. These micro-dimensionedchannels may have heights in the range from about 0.05 to about 10 mm,and in one embodiment from about 0.05 to about 5 mm, and widths in therange from about 0.05 to about 1 mm, and in one embodiment from about0.05 to about 0.25 mm. The heights and widths may be aligned normal tothe flow of fluid in the micro-dimensioned channels. The cross-sectionalarea of the flow distribution feature may be up to about 100 timessmaller than the cross-sectional area of the process microchannel it isconnected to, and in one embodiment up to about 50 times smaller, and inone embodiment up to about 10 times smaller, and in one embodiment up toabout 2 times smaller. These micro-dimensioned channels may be usefulwhen the pressure drops provided by the different feed streams flowingfrom the manifolds to the process microchannels are different. Forexample, the pressure drop for feed stream A may be three times smallerthan the pressure drop for the feed stream B and flow distributionfeatures may be used for the feed with the smaller pressure drop.Alternatively, flow resistors may be used for the feed streams with thelower pressure drops.

The feed streams may enter the microchannel processing unit 100 using across-flow orientation as illustrated in FIG. 65. Both feed streams Aand B may enter the microchannel processing unit using one or morestraight flow through inlet manifolds. This microchannel processing unitmay be constructed using alternating shims and orifice plates asillustrated in FIG. 63, with the exception that the feed streams flowdirectly into the process microchannels, rather than through manifoldsrequiring at least one turn in the direction of flow as illustrated inFIG. 63.

Flow resistors and/or flow distribution features in the manifolds may beused to reduce sensitivities to manufacturing tolerances. The flowresistors and/or flow distribution features may reduce the sensitivityof overall pressure drop to manufacturing tolerance variations. Tighttolerances for manufacturing flow resistors and/or flow distributionfeatures may be achieved by etching the flow resistors and/or flowdistribution features in shims made from the same stock.

A plurality of the microchannel processing units 100 may be housed invessel 600 which is illustrated in FIGS. 50 and 51. Referring to FIGS.50 and 51, the vessel 600 contains five microchannel processing units100. These are identified in FIGS. 50 and 51 as microchannel processingunits 100-1, 100-2, 100-3, 100-4 and 100-5. Although five microchannelprocessing units 100 are disclosed in the drawings, it will beunderstood that the vessel 600 may contain any desired number ofmicrochannel processing units. For example, the vessel 600 may containfrom 1 to about 1000 microchannel processing units 100, and in oneembodiment from about 3 to about 500 microchannel processing units 100,and in one embodiment from about 3 to about 250 microchannel processingunits 100, and in one embodiment from about 3 to about 150 microchannelprocessing units 100, and in one embodiment from about 5 to about 50microchannel processing units 100, and in one embodiment from about 5 toabout 12 microchannel processing units 100. In one embodiment, thevessel 600 may contain from 1 to about 50 microchannel processing units100, and in one embodiment from 1 to about 20 microchannel processingunits 100. Each microchannel processing unit 100 may comprise from about1 to about 50,000 process microchannels, and in one embodiment fromabout 10 to about 50,000 process microchannels, and in one embodimentfrom about 10 to about 30,000, and in one embodiment from about 10 toabout 10,000 process microchannels. The vessel 600 may be apressurizable vessel. The vessel 600 includes inlets 602 and 604, andoutlets 606 and 608. The inlet 602 is connected to a manifold which maybe provided for flowing the first fluid to the process microchannels inthe microchannel processing units 100-1, 100-2, 100-3, 100-4 and 100-5.The inlet 604 is connected to a manifold which may be provided forflowing heat exchange fluid to the heat exchange channels in themicrochannel processing units 100-1, 100-2, 100-3, 100-4 and 100-5. Theoutlet 706 is connected to a manifold which may be provided for flowingproduct from the microchannel processing units 100-1, 100-2, 100-3,100-4 and 100-5 out of the vessel 600. The inlet 608 is connected to amanifold which may provide for the flow of the second fluid to stagedaddition channels that may be in the microchannel processing units100-1, 100-2, 100-3, 100-4 and 100-5. The vessel 600 also includes anoutlet (not shown in the drawings) providing for the flow of heatexchange fluid from the microchannel processing units 100-1, 100-2,100-3, 100-4 and 100-5.

The vessel 600 may be constructed from any suitable material sufficientfor operating under the pressures and temperatures required foroperating the microchannel reactors. For example, the shell and heads ofthe vessels 600 may be constructed of cast steel. The flanges, couplingsand pipes may be constructed of stainless steel or other suitablealloys. The vessel 600 may have any desired diameter, for example, fromabout 30 to about 500 cm, and in one embodiment from about 100 to about300 cm. The axial length of the vessel 600 may be of any desired value,for example, from about 0.5 to about 50 meters, and in one embodimentfrom about 0.5 to about 15 meters, and in one embodiment from about 1 toabout 10 meters.

As indicated above, the microchannel processing units 100 may comprise aplurality of process microchannels, heat exchange channels andoptionally staged addition channels stacked one above the other orpositioned side-by-side. The microchannel processing units 100 may be inthe form of cubic blocks as illustrated in FIGS. 50 and 51. Each ofthese cubic blocks may have a length, width and height. The length maybe in the range from about 10 to about 1000 cm, and in one embodiment inthe range from about 50 to about 200 cm. The width may be in the rangefrom about 10 to about 1000 cm, and in one embodiment in the range fromabout 50 to about 200 cm. The height may be in the range from about 10to about 1000 cm, and in one embodiment in the range from about 50 toabout 200 cm.

The inventive process may be suitable for conducting any chemicalreaction wherein one or more of the reactants and/or products is annon-Newtonian fluid. These may include gas-liquid reactions,liquid-liquid reactions, gas-liquid-liquid reactions, gas-liquid-solidreactions, liquid-liquid-solid reactions, and the like. The reactionsthat may be conducted in accordance with the inventive process mayinclude any fluid reaction including oxidation reactions, hydrocrackingreactions, hydrogenation reactions, hydration reactions, carbonylationreactions, sulfation reactions, sulfonation reactions, oligomerizationreactions, polymerization reactions, and the like.

A first reactant may comprise one or more liquids. When the firstreactant comprises more than one liquid, the resulting liquid mixturemay be in the form of a solution or a multiphase fluid mixture (forexample, an emulsion). The first reactant may comprise solids dispersedin one or more of the fluids. The solids may comprise catalyticparticulates. Alternatively the solids may not be catalytic. The solidsmay be added to provide a desired product texture, adsorb wanted orunwanted by-products, intensify shear with the process microchannel,etc. The solids may be of any size provided they are small enough to bein the process microchannels. For example, the solids may have a medianparticle diameter in the range from about 0.01 to about 200 microns, andin one embodiment from about 1 to about 40 microns.

A second reactant may comprise one or more liquids, one or more gases,or a mixture thereof. The second reactant may comprise one or more gasescontaining dispersed liquid droplets or one or more liquids containingdispersed gas bubbles. The second reactant, when in the form of a gasand introduced into the first reactant to form a multiphase reactionmixture, may form gas bubbles in the first reactant. The secondreactant, when in the form of a liquid and introduced into the firstreactant to form a multiphase reaction mixture, may form liquid dropletsin the first reactant. When in liquid form, the second reactant may beimmiscible with the first reactant. Alternatively, the multiphasereaction mixture may comprise a foam where a thin liquid film coversentrapped gas. The foam may comprise a continuous or discontinuous foamstructure.

The purity of the reactants may not be critical, though it is desirableto avoid the presence of compounds which may poison the catalyst. Thereactants may comprise impurities that are not reactive with thereactants.

The first and/or second reactants may be combined with one or morediluent materials. Examples of such diluents include nitrogen, helium,non-reactive hydrocarbon diluents, and the like. The diluentconcentration of each of the reactants may range from zero to about 99%by weight, and in one embodiment from zero to about 75% by weight, andin one embodiment from zero to about 50% by weight. Diluents may becombined with one or more of the reactants when the reactant is ingaseous form and it is desired to use a liquid as the reactant. Diluentsmay be used to reduce the viscosity of viscous liquid reactants. Anadvantage of at least one embodiment of the invention is that withoutthe use of such diluents a more efficient and compact process may beprovided.

The catalyst may be an oxidation catalyst, hydrocracking catalyst,hydrogenation catalyst, hydration catalyst, carbonylation catalyst,sulfation catalyst, sulfonation catalyst, oligomerization catalyst,polymerization catalyst, or a combination of two or more thereof.

The oxidation reactions may involve the reaction, in the presence of oneor more oxidation catalysts, of one or more hydrocarbon compounds thatare capable of undergoing an oxidation reaction with oxygen or a sourceof oxygen. The hydrocarbon compounds, which may be referred to as thefirst reactant, may be in the form of liquids, or they may be in theform of gases dispersed in one or more liquids. The oxygen or oxygensource, which may be referred to as the second reactant, may be in theform of a gas.

The hydrocarbon compounds that may be used in the oxidation reactionsinclude saturated aliphatic compounds (e.g., alkanes), unsaturatedaliphatic compounds (e.g., alkenes, alkynes), aldehydes, alkylsubstituted aromatic compounds, alkylene substituted aromatic compounds,and the like. The saturated aliphatic compounds include alkanescontaining 1 to about 25 carbon atoms per molecule, and in oneembodiment 1 to about 20 carbon atoms, and in one embodiment 1 to about10 carbon atoms. These include straight chain alkanes, single andmultiple branched chain alkanes, and cyclic alkanes including cyclicalkanes having one or more alkyl groups attached to the ring. Theseinclude methane, ethane, propane, isopropane, butane, isobutane,pentane, cyclopentane, hexane, heptane, octane, 2-ethylhexane, nonane,decane, dodecane, and the like. The unsaturated aliphatic compoundsinclude alkenes or alkylenes, and alkynes. The unsaturated aliphaticcompounds may contain from 2 to about 25 carbon atoms, and in oneembodiment about 2 to about 20 carbon atoms, and in one embodiment about2 to about 10 carbon atoms. These include straight chain alkenes, singleand multiple branched chain alkenes, and cyclic alkenes including cyclicalkenes having one or more alkyl and/or alkene groups attached to thering. These include ethylene; propylene; 1-butene; 2-butene;isobutylene; 1-pentene; 2-pentene; 3-methyl-1-butene; 2-methyl-2-butene;1-hexene; 2,3-dimethyl-2-butene; 1-heptene; 1-octene; 1-nonene;1-decene; 1-dodecene; and the like.

The unsaturated aliphatic compounds may comprise polyenes. These includedienes, trienes, and the like. These compounds may contain from 3 toabout 25 carbon atoms per molecule, and in one embodiment 3 to about 20carbon atoms, and in one embodiment about 3 to about 10 carbon atoms.Examples include 1,2-propadiene (also known as allene); 1,3-butadiene;2-methyl-1,3-butadiene (also known as isoprene); 1,3-pentadiene;1,4-pentadiene; 1,5-hexadiene; 2,4-hexadiene;2,3-dimethyl-1,3-butadiene; and the like.

The aldehydes may be saturated or unsaturated. They may be aliphaticand/or aromatic. The aldehydes may contain from 2 to about 25 carbonatoms per molecule, and in one embodiment about 2 to about 20 carbonatoms, and in one embodiment about 2 to about 10 carbon atoms. Examplesinclude formaldehyde; acetaldehyde; propionaldehyde; n-butyraldehyde;n-valeraldehyde; caproaldehyde; acrolein; tran-2-cis-6-nonadienal;n-heptylaldehyde; trans-2-hexenal; hexadeconal; benzaldehyde;phenylacetaldehyde; o-tolualdehyde; m-tolualdehyde; p-tolualdehyde;salicylaldehyde; p-hydroxybenzaldehyde; and the like.

The alkyl or alkylene substituted aromatic compounds may contain one ormore alkyl or alkylene substituents. These compounds may be monocyclic(e.g., phenyl) or a polycyclic (e.g., naphthyl). These compounds includealkyl substituted aromatic compounds containing one or more alkyl groupscontaining 1 to about 25 carbon atoms, and in one embodiment 1 to about20 carbon atoms, and in one embodiment 1 to about 10 carbon atoms. Thesealso include the alkylene substituted aromatic compounds containing oneor more alkylene groups containing 2 to about 25 carbon atoms, and inone embodiment 2 to about 20 carbon atoms, and in one embodiment 2 toabout 10 carbon atoms. Examples include toluene, o-xylene, m-xylene,p-xylene, hemimellitene, pseudocumene, mesitylene, prehnitene,isodurene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene,n-propylbenzene, cumene, n-butylbenzene, isobutylbenzene,sec-butylbenzene, tert-butylbenzene, p-cymene, styrene, and the like.

The oxygen or oxygen source used in the oxidation reactions may comprisemolecular oxygen, air or other oxidants, such as nitrogen oxides, whichcan function as a source of oxygen. The oxygen source may be carbondioxide, carbon monoxide or a peroxide (e.g., hydrogen peroxide).Gaseous mixtures containing oxygen, such as mixtures of oxygen and air,or mixtures of oxygen and an inert gas (e.g., helium, argon, etc.) or adiluent gas (e.g., carbon dioxide, water vapor, etc.) may be used. Theoxygen source may comprise oxygen enriched air.

The mole ratio of the hydrocarbon reactant to oxygen may be in the rangefrom about 0.2:1 to about 8:1, and in one embodiment about 0.5:1 toabout 4:1, and in one embodiment about 1:1 to about 3:1. In oneembodiment, the mole ratio may be about 2:1 or higher, and in oneembodiment about 2.5:1 or higher. In one embodiment, the mole ratio maybe about 1.8 or less.

The oxidation catalyst may comprise any catalyst that is useful as anoxidation catalyst. The catalyst may comprise a metal, metal oxide ormixed metal oxide of one or more of Mo, W, V, Nb, Sb, Sn, Pt, Pd, Cs,Zr, Cr, Mg, Mn, Ni, Co, Ce, or a mixture of two or more thereof. Thesecatalysts may also comprise one or more alkali metals or alkaline earthmetals or other transition metals, rare earth metals, or lanthanides.Additionally elements such as P and Bi may be present. The catalyst maybe supported, and if so, useful support materials include metal oxides(e.g., alumina, titania, zirconia), silica, mesoporous materials,zeolites, refractory materials, or combinations of two or more thereof.The form which these catalysts may be in is discussed in greater detailbelow.

The product formed by the oxidation reaction may comprise one or moreoxygenates. The term “oxygenate” is used herein to refer to ahydrocarbon compound that contains at least one oxygen. The oxygenatesinclude alcohols, epoxides, aldehydes, ketones, carboxylic acids,carboxylic acid anhydrides, esters, and the like. The oxygenatesinclude, with the exception of the epoxides and esters, one or more ofthe above-indicated oxygenates containing 1 to about 25 carbon atoms permolecule, and in one embodiment 1 to about 20 carbon atoms, and in oneembodiment 1 to about 10 carbon atoms. The epoxides and esters mustcontain at least 2 carbon atoms, but in all other respects would includecompounds within the above-indicated ranges, for example, 2 to about 25carbon atoms, etc. The alcohols include monools and polyols. Specificexamples include methanol, ethyl alcohol, propyl alcohol, butyl alcohol,isobutyl alcohol, pentyl alcohol, cyclopentyl alcohol, crotyl alcohol,hexyl alcohol, cyclohexyl alcohol, allyl alcohol, benzyl alcohol,glycerol, and the like. The epoxides include ethylene oxide, propyleneoxide, butylene oxide, isobutylene oxide, cyclopentene oxide,cyclohexene oxide, styrene oxide, and the like. The aldehydes includeformaldehyde; acetaldehyde; propionaldehyde; n-butyraldehyde;n-valeraldehyde; caproaldehyde; acrolein; tran-2-cis-6-nonadienal;n-heptylaldehyde; trans-2-hexenal; hexadeconal; benzaldehyde;phenylacetaldehyde; o-tolualdehyde; m-tolualdehyde; p-tolualdehyde;salicylaldehyde; p-hydroxybenzaldehyde; and the like. The ketonesinclude acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone,2-hexanone, 3-hexanone, cyclohexanone, methyl isobutyl ketone,acetophenone, propiophenone, n-butyrophenone, benzophenone, and thelike. The carboxylic acids include formic acid, acetic acid, propionicacid, butyric acid, isobutyric acid, valeric acid, caproic acid,caprylic acid, capric acid, acrylic acid, methacrylic acid, benzoicacid, toluic acid, phthalic acid, salicylic acid, and the like. Thecarboxylic acid anhydrides include acetic anhydride, maleic anhydride,phthalic anhydride, benzoic anhydride, and the like. The carboxylicacids and anhydrides include hydrocarbon substituted carboxylic acidsand anhydrides (e.g., hydrocarbon substituted succinic acids andanhydrides) wherein the hydrocarbon substituent contains from 1 to about500 carbon atoms, and in one embodiment about 20 to about 500 carbonatoms. The esters include methyl acetate, vinyl acetate, ethyl acetate,n-propyl acetate, n-butyl acetate, n-pentyl acetate, isopentyl acetate,benzyl acetate, phenyl acetate, and the like.

The hydrocracking reactions may involve destructive hydrogenation (alsoknown as hydrogenolysis) of large hydrocarbon molecules wherein thelarge or heavy hydrocarbon molecules are broken down to smaller orlighter ones and reacted with hydrogen. The hydrocarbon reactant may bereferred to as the first reactant and the hydrogen may be referred to asthe second reactant. The terms “light” and “heavy” are used herein intheir normal sense within the refining industry to refer respectively torelatively low and high boiling point ranges. The hydrocarbon reactantmay comprise any hydrocarbon requiring hydrocracking. The hydrocarbonreactant may vary from naptha to heavy crude oil residual fractions. Thehydrocarbon reactant may have a 5% by volume boiling point above about350° F. (177° C.), and in one embodiment above about 400° F. (204° C.).In one embodiment, at least about 90% by volume of the hydrocarbonreactant may fall within the boiling point range of about 300° F. (149°C.) to about 1050° F. (566° C.), and in one embodiment between about600° F. (316° C.) to about 1000° F. (538° C.). The hydrocarbon reactantmay comprise one or more petroleum fractions such as atmospheric andvacuum gas oils (AGO and VGO).

The hydrocarbon reactant may comprise heavy hydrocarbonaceous mineral orsynthetic oils or a mixture of one or more fractions thereof. Thehydrocarbon reactant may comprise one or more straight run gas oils,vacuum gas oils, demetallized oils, deasphalted vacuum residues, cokerdistillates, cat cracker distillates, shale oils, tar sand oils, coalliquids, or a mixture of two or more thereof.

The hydrogen used in the hydrocracking reactions may be in the form ofhydrogen gas or it may be in a hydrogen feed stream that furthercomprises water, methane, carbon dioxide, carbon monoxide and/ornitrogen. The hydrogen may be taken from a process stream of anotherprocess such as a steam reforming process (product stream with H₂/COmole ratio of about 3), a partial oxidation process (product stream withH₂/CO mole ration of about 2), an autothermal reforming process (productstream with H₂/CO mole ratio of about 2.5), a CO₂ reforming process(product stream with H₂/CO mole ratio of about 1), a coal gasificationprocess (product stream with H₂/CO mole ratio of about 1), andcombinations thereof. With each of these hydrogen sources, the hydrogenmay be separated from the remaining ingredients using conventionaltechniques such as membrane separation or adsorption.

The mole ratio of hydrocarbon reactant to hydrogen in thesehydrocracking reactions may be in the range from about 0.1:1 to about10:1, and in one embodiment about 0.5:1 to about 5:1.

The hydrocracking catalyst may be any hydrocracking catalyst. Theseinclude zeolite catalysts including beta zeolite, omega zeolite,L-zeolite, ZSM-5 zeolites and Y-type zeolites. The catalyst may includea refractory inorganic oxide such as alumina, magnesia, silica, tilania,zirconia and silica-alumina. The catalyst may comprise a hydrogenationcomponent. Examples of suitable hydrogenation components include metalsof Group IVB and Group VIII of the Periodic Table and compounds of suchmetals. Molybdenum, tungsten, chromium, iron, cobalt, nickel, platinum,palladium, iridium, osmium, rhoduim and ruthenium may be used as thehydrogenation component. These catalysts are described in U.S. Pat. No.6,312,586 B1, which is incorporated herein by reference.

The product made by the hydrocracking process may be a middle distillatefraction boiling in the range from about 260 to about 700° F. (127-371°C.). The term “middle distillate” is intended to include the diesel, jetfuel and kerosene boiling range fractions. The terms “kerosene” and “jetfuel” boiling range are intended to refer to a temperature range of260-550° F. (127-288° C.) and “diesel” boiling range is intended torefer to hydrocarbon boiling points from about 260 to about 700° F.(127-371° C.). The distillate product may be a gasoline or naphthafraction. These may be considered to be the C₅ to 400° F. (204° C.)endpoint fractions.

The hydrogenation reactions may involve the reaction, in the presence ofone or more hydrogenation catalysts, of one or more hydrocarboncompounds that are capable of undergoing a hydrogenation reaction withhydrogen. The hydrocarbon compounds may be referred to as the firstreactant. These hydrocarbon compounds may be in the form of liquids, orthey may be in the form of gases dispersed in liquids. The liquid maycomprise the reactant and one or more additional solvents. The solventsmay be solvents for one or more reactants and/or products. The hydrogenmay be referred to as the second reactant, and may be in the form of agas. The hydrogen may be derived from any of the above mentionedsources.

The hydrocarbon compounds that may undergo a hydrogenation reactioninclude the unsaturated hydrocarbon compounds discussed above. Thehydrocarbon compounds include unsaturated fats and oils. The fats andoils may be derived from animal or vegetable sources. The fats and oilsinclude triglycerides, that is, esters of glycerol and fatty acids. Thefatty acids may be monounsaturated or polyunsaturated. Examples of thefatty acids in the fats and oils include oleic acid, linoleic acid,linolenic acid, and the like.

The mole ratio of unsaturated hydrocarbon reactant to hydrogen in thesehydrogenation reactions may be in the range from about 0.1:1 to about10:1, and in one embodiment about 0.5:1 to about 5:1.

The hydrogenation catalyst may be hydrogenation any catalyst. Theseinclude metals of Group IVB and Group VIII of the Periodic Table andcompounds of such metals. Molybdenum, tungsten, chromium, iron, cobalt,nickel, platinum, palladium, iridium, osmium, rhodium, rhenium, andruthenium may be used. In one embodiment, the catalyst may comprisepalladium coated on the walls of the process microchannel or adhered toa fixed support within the process microchannel. The form in which thesecatalysts may be in is discussed in greater detail below.

The product made by the hydrogenation process may be a saturated orpartially saturated hydrocarbon corresponding to the unsaturatedhydrocarbon compounds used as the first reactant.

The process may be used to hydrogenate vegetable oils to increase theirdegree of saturation to produce edible fat products such as margarines.The improved mass transfer resulting from the inventive process may alsoimprove the selectivity of the process to reduce the amount of unwantedconversion of cis isomers of triglycerides to trans isomers. Thisinvention may improve the formation of the trans isomer from about 30%to about 50% by weight which may be obtained using conventionaltechnology (i.e., non-microchannel process technology) to less thanabout 15% by weight, and in one embodiment less than about 10% byweight, and in one embodiment less than about 8% by weight. The processmay use a hydrogenation catalyst. The catalyst may be in the form of aslurry, particulate solids or a fixed bed.

In one embodiment, the hydrogenation process may involve use of acatalyst (for example a precious metal such as palladium) fixed on theinterior walls of the process microchannels or on a support structurepositioned within the process microchannels. This may eliminate the needfor a filtration step. This may also result in safer (no catalystcontamination), higher purity products. Precious metals catalysts suchas palladium may be more reactive than prior art nickel catalysts and assuch may effect the hydrogenation reactions at lower temperatures thanconventionally used. This combined with the improved heat transferresulting from the inventive process may significantly reduce theformation of secondary products that typically form as a result ofthermal decomposition of oils and fats. This also may improve thequality of the food product. Unlike conventional nickel catalysts, theuse of a palladium catalyst at reduced hydrogenation temperatures maydecrease the concentration of hazardous trans-isomers, especially usinghigh conversions which may be achieved at relatively short contact timespursuant to the inventive process. Improved mass transfer resulting fromthe inventive process may also improve the selectivity of the process.Improved heat and mass transfer may improve catalyst stability andturn-over frequency. This may result in a lower catalyst requirement.This may be beneficial when using precious metals because of the lowoperating temperature and pressure. In one embodiment, the catalyst maycomprise nano-scale size particles of a precious metal such as palladiumdispersed on the walls of the process microchannels and/or surfacefeatures or on a catalytic support such as a fin assembly insert using adispersing/binding agent such as a colloidal metal oxide, carbon black,furfural alcohol, etc. The catalyst may be made using micro-shapescoated with catalytic metals that fill the void space of themicrochannels.

The hydration reactions may involve the reaction, in the presence of ahydration catalyst, of an unsaturated hydrocarbon compound with water toform an alcohol or an ether. The unsaturated hydrocarbon compound, whichmay be referred to as the first reactant, may be any of the unsaturatedhydrocarbon compounds discussed above. The water, which may be referredto as the second reactant, may be taken from any convenient source. Thewater may be deionized or purified using osmosis or distillation. Themole ratio of unsaturated hydrocarbon to water may be in the range fromabout 0.1 to about 10, and in one embodiment about 0.5 to about 5.

The hydration catalyst may comprise a solid acid catalyst such aszeolite; an acidic ion exchange resin containing sulfonate groups or thelike; an inorganic oxide such as hydrated niobium oxide, hydratedtantalum oxide, zirconium dioxide, titanium dioxide, aluminum oxide,silicon dioxide, or a mixed oxide thereof; or an ion exchange typelayered compound obtained by treating a layered compound such assmectite, kaolinite or vermiculite with at least one metal oxideselected from oxides of aluminum, silicon, titanium and zirconium. Thecatalyst may comprise aluminosilicates such as mordenite, faujasite,clinoptilite, L type zeolite, chabazite, erionite and ferrierite, aswell as zeolite products ZSM-5, ZSM-4, ZSM-8, ZSM-11, ZSM-12, ZSM-20,ZSM-40, ZSM-35 and ZSM-48. The catalyst may comprise anelement-containing zeolite such as borosilicate, gallosilicate andferroaluminosilicate. These zeolites may contain thorium, copper,silver, chromium, molybdenum, tungsten, titanium, zirconium, hafnium andlike metals. A proton exchange type (H type) zeolite may be used, and aportion thereof may be exchanged with a cationic species selected fromalkali elements such as Na, K and Li, alkaline earth elements such asMg, Ca and Sr and Group VIII elements such as Fe, Co, Ni, Ru or Pd. Theform in which the catalyst may be in is discussed in greater detailbelow.

The carbonylation reactions may involve the reaction of a saturated orunsaturated hydrocarbon with carbon monoxide in the presence of acarbonylation catalyst. The saturated or unsaturated hydrocarbonreactant, which may be referred to as the first reactant, may be any ofthe saturated or unsaturated hydrocarbons discussed above. The carbonmonoxide, which may be referred to as the second reactant, may be takenfrom any source. The carbon monoxide may be taken from a process streamsuch as a steam reforming process (product stream with H₂/CO mole ratioof about 3), a partial oxidation process (product stream with H₂/CO moleratio of about 2), an autothermal reforming process (product stream withH₂/CO mole ratio of about 2.5), a CO₂ reforming process (product streamwith H₂/CO mole ratio of about 1), a coal gasification process (productstream with H₂/CO mole ratio of about 1), and combinations thereof. Witheach of these carbon monoxide sources, the carbon monoxide may beseparated from the remaining ingredients using conventional techniquessuch as membranes or adsorption.

The mole ratio of hydrocarbon reactant to carbon monoxide in thesecarbonylation reactions may be in the range from about 0.5:1 to about20:1, and in one embodiment about 2:1 to about 10:1.

The carbonylation catalyst may be any carbonylation catalyst. Theseinclude solid acid catalysts. The catalyst may be a solid comprisinginteracting protic and Lewis acid sites. The catalyst may comprise acombination of a Bronsted (protonic) acid and a Lewis acid. Examplesinclude sulfated metal oxides (e.g., sulfated zirconia), fluorocarbonsulfonates (B(CF₂)_(n)BSO₃H) in combination with supports (e.g., metaloxides and carbon), heteropolyacids, halides of Ta, Sb, Ga and B,halogenated metal oxides, sulfated zeolites, halides of Ta, Sb, Ga and Bin combination with fluorosulfonic acid resins. The metal oxides includeboth single component oxides and multi-component oxides, i.e., mixedmetal oxides. Single component metal oxides include aluminas, silicas,zirconia, titania and mixtures thereof. The mixed metal oxides can beeither physical mixtures or structurally connected. Example of mixedmetal oxides include ZrCTi, WCZr, TiCCu, TiCZn, TiCSi, AlCZr, FeCZr andTiCMn oxides. Examples include sulfated zirconia, sulfated titania,sulfated tungsten oxide, BF₃ on fluorinated alumina, aluminum chlorideon chlorinated alumina, H₃PW₁₀O₄₀, Cs_(2.5)H_(0.5)PW₁₂O₄₀, H₄SiW₁₂O₄₀,and the like. The form in which the catalyst may be in is discussed ingreater detail below.

The sulfonation reactions may involve the substitution of —SO₃H groups(from sulfuric acid) for hydrogen atoms, for example, conversion ofbenzene, C₆H₆, into benzenesulfonic acid, C₆H₆SO₃H. The sulfonationprocedures that may be used include the reaction of aromatichydrocarbons with sulfuric acid, sulfur trioxide, or chlorosulfuricacid; the reaction of organic halogen compounds with inorganic sulfites;and the oxidation of certain classes of organic sulfur compounds, forexample, thiols or disulfides.

Concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid,sulfuric anhydride, adducts of dioxane with SO₃, adducts of amine withSO₃, etc. may be used as agents for sulfonating aromatic compounds byintroducing a sulfonic acid group into the aromatic ring of thecompound. Aromatic amine compounds may be sulfonated by preparing anacidic sulfate of amine from the aromatic amine compound and astoichiometric amount of sulfuric acid and heated to obtain anaminesulfonic acid.

The sulfation reactions may involve methods by which esters or salts ofsulfuric acid (sulfates) are formed. The esters may be prepared bytreating an alcohol with sulfuric acid, sulfur trioxide, chlorosulfuricacid, or sulfamic acid. The sulfating agents may include concentratedsulfuric acid, oleum, sulfur trioxide, chlorosulfonic acid, or sulfamicacid.

The polymerization reaction may be any polymerization reaction suitablefor forming any of the polymers discussed above. The catalyst used inthese reactions may be any suitable polymerization catalyst for makingthe indicated polymer. Examples of catalysts that may be used mayinclude Lewis acids such as BF₃, organolithium catalysts such as butyllithium, Grignard reagents, Ziegler-Natta catalysts, and the like.

The catalyst for the reactions conducted in accordance with theinventive process may be a homogeneous catalyst or a heterogeneouscatalyst. The homogeneous catalyst may be immobilized on a support. Thecatalyst may have any size and geometric configuration that fits withinthe process microchannels. The catalyst may be a graded catalyst.

The catalyst may be in the form of particulate solids (e.g., pellets,powder, fibers, and the like) having a median particle diameter of about1 to about 1000 microns, and in one embodiment about 10 to about 500microns, and in one embodiment about 25 to about 250 microns.

The catalyst may be in the form of a mesoporous material wherein theaverage pore size may be at or above about 1 nanometer (nm), forexample, in the range from about 1 to about 100 nm, and in oneembodiment from about 1 to about 20 nm.

The catalyst may be in the form of a fixed bed of particulate solidssuch as illustrated in FIG. 35. Referring to FIG. 35, the catalyst 350is contained within process microchannel 352. The reactants flow throughthe catalyst bed as indicated by arrows 354 and 356.

The catalyst may be supported on a porous support structure such as afoam, felt, wad or a combination thereof. The term “foam” is used hereinto refer to a structure with continuous walls defining pores throughoutthe structure. The term “felt” is used herein to refer to a structure offibers with interstitial spaces therebetween. The term “wad” is usedherein to refer to a support having a structure of tangled strands, likesteel wool. The catalyst may be supported on a support having ahoneycomb structure or a serpentine configuration.

The catalyst may be supported on a flow-by support structure such as afelt with an adjacent gap, a foam with an adjacent gap, a fin structurewith gaps, a washcoat on any inserted substrate, or a gauze that isparallel to the flow direction with a corresponding gap for flow. Anexample of a flow-by structure is illustrated in FIG. 36. In FIG. 36 thecatalyst 360 is contained within process microchannel 362. An openpassage way 364 permits the flow of the reactants through the processmicrochannel 362 in contact with the catalyst 360 as indicated by arrows366 and 368.

The catalyst may be supported on a flow-through support structure suchas a foam, wad, pellet, powder, or gauze. An example of a flow-throughstructure is illustrated in FIG. 37. In FIG. 37, the flow-throughcatalyst 370 is contained within process microchannel 372 and thereactants flow through the catalyst 370 as indicated by arrows 374 and376.

The support may be formed from a material comprising silica gel, foamedcopper, sintered stainless steel fiber, steel wool, alumina, poly(methylmethacrylate), polysulfonate, poly(tetrafluoroethylene), iron, nickelsponge, nylon, polyvinylidene difluoride, polypropylene, polyethylene,polyethylene ethylketone, polyvinyl alcohol, polyvinyl acetate,polyacrylate, polymethylmethacrylate, polystyrene, polyphenylenesulfide, polysulfone, polybutylene, or a combination of two or morethereof. In one embodiment, the support structure may be made of a heatconducting material, such as a metal, to enhance the transfer of heataway from the catalyst.

The catalyst may be directly washcoated on the interior walls of theprocess microchannels, grown on the walls from solution, or coated insitu on a fin structure. The catalyst may be coated on structured wallssuch as illustrated in FIGS. 48-49. The catalyst may be coated onsurface features such as those illustrated in FIGS. 46-47. The catalystmay be in the form of a single piece of porous contiguous material, ormany pieces in physical contact. In one embodiment, the catalyst maycomprise a contiguous material and have a contiguous porosity such thatmolecules can diffuse through the catalyst. In this embodiment, thefluids may flow through the catalyst rather than around it. In oneembodiment, the cross-sectional area of the catalyst may occupy fromabout 1 to about 99%, and in one embodiment from about 10 to about 95%of the cross-sectional area of the process microchannels. The catalystmay have a surface area, as measured by BET, of greater than about 0.5m²/g, and in one embodiment greater than about 2 m²/g, and in oneembodiment greater than about 5 m²/g, and in one embodiment greater thanabout 10 m²/g, and in one embodiment greater than about 25 m²/g, and inone embodiment greater than about 50 m²/g.

The catalyst may comprise a porous support, an interfacial layeroverlying the porous support, and a catalyst material dispersed ordeposited on the interfacial layer. The interfacial layer may besolution deposited on the support or it may be deposited by chemicalvapor deposition or physical vapor deposition. In one embodiment thecatalyst comprises a porous support, optionally a buffer layer overlyingthe support, an interfacial layer overlying the support or the optionalbuffer layer, and a catalyst material dispersed or deposited on theinterfacial layer. Any of the foregoing layers may be continuous ordiscontinuous as in the form of spots or dots, or in the form of a layerwith gaps or holes.

The porous support may have a porosity of at least about 5% as measuredby mercury porosimetry and an average pore size (sum of pore diametersdivided by number of pores) of about 1 to about 1000 microns. The poroussupport may be made of any of the above indicated materials identifiedas being useful in making a support structure. The porous support maycomprise a porous ceramic support or a metal foam. Other porous supportsthat may be used include carbides, nitrides, and composite materials.The porous support may have a porosity of about 30% to about 99%, and inone embodiment about 60% to about 98%. The porous support may be in theform of a foam, felt, wad, or a combination thereof. The open cells ofthe metal foam may range from about 20 pores per inch (ppi) to about3000 ppi, and in one embodiment about 20 to about 1000 ppi, and in oneembodiment about 40 to about 120 ppi. The term “ppi” refers to thelargest number of pores per inch (in isotropic materials the directionof the measurement is irrelevant; however, in anisotropic materials, themeasurement is done in the direction that maximizes pore number).

The buffer layer, when present, may have a different composition and/ordensity than both the porous support and the interfacial layers, and inone embodiment has a coefficient of thermal expansion that isintermediate the thermal expansion coefficients of the porous supportand the interfacial layer. The buffer layer may be a metal oxide ormetal carbide. The buffer layer may be comprised of Al₂O₃, TiO₂, SiO₂,ZrO₂, or combination thereof. The Al₂O₃ may be α-Al₂O₃, γ-Al₂O₃ or acombination thereof. α-Al₂O₃ provides the advantage of excellentresistance to oxygen diffusion. The buffer layer may be formed of two ormore compositionally different sublayers. For example, when the poroussupport is metal, for example a stainless steel foam, a buffer layerformed of two compositionally different sub-layers may be used. Thefirst sublayer (in contact with the porous support) may be TiO₂. Thesecond sublayer may be α-Al₂O₃ which is placed upon the TiO₂. In oneembodiment, the α-Al₂O₃ sublayer is a dense layer that providesprotection of the underlying metal surface. A less dense, high surfacearea interfacial layer such as alumina may then be deposited as supportfor a catalytically active layer.

The porous support may have a thermal coefficient of expansion differentfrom that of the interfacial layer. In such a case a buffer layer may beneeded to transition between the two coefficients of thermal expansion.The thermal expansion coefficient of the buffer layer can be tailored bycontrolling its composition to obtain an expansion coefficient that iscompatible with the expansion coefficients of the porous support andinterfacial layers. The buffer layer should be free of openings and pinholes to provide superior protection of the underlying support. Thebuffer layer may be nonporous. The buffer layer may have a thicknessthat is less than one half of the average pore size of the poroussupport. The buffer layer may have a thickness of about 0.05 to about 10μm, and in one embodiment about 0.05 to about 5 μm.

In one embodiment of the invention, adequate adhesion and chemicalstability may be obtained without a buffer layer. In this embodiment thebuffer layer may be omitted.

The interfacial layer may comprise nitrides, carbides, sulfides,halides, metal oxides, carbon, or a combination thereof. The interfaciallayer provides high surface area and/or provides a desirablecatalyst-support interaction for supported catalysts. The interfaciallayer may be comprised of any material that is conventionally used as acatalyst support. The interfacial layer may be comprised of a metaloxide. Examples of metal oxides that may be used include γ-Al₂O₃, SiO₂,ZrO₂, TiO₂, tungsten oxide, magnesium oxide, vanadium oxide, chromiumoxide, manganese oxide, iron oxide, nickel oxide, cobalt oxide, copperoxide, zinc oxide, molybdenum oxide, tin oxide, calcium oxide, aluminumoxide, lanthanum series oxide(s), zeolite(s) and combinations thereof.The interfacial layer may serve as a catalytically active layer withoutany further catalytically active material deposited thereon. Usually,however, the interfacial layer is used in combination with acatalytically active layer. The interfacial layer may also be formed oftwo or more compositionally different sublayers. The interfacial layermay have a thickness that is less than one half of the average pore sizeof the porous support. The interfacial layer thickness may range fromabout 0.5 to about 100 μm, and in one embodiment from about 1 to about50 μm. The interfacial layer may be either crystalline or amorphous. Theinterfacial layer may have a BET surface area of at least about 1 m²/g.

The catalyst may be deposited on the interfacial layer. Alternatively,the catalyst material may be simultaneously deposited with theinterfacial layer. The catalyst layer may be intimately dispersed on theinterfacial layer. That the catalyst layer is “dispersed on” or“deposited on” the interfacial layer includes the conventionalunderstanding that microscopic catalyst particles are dispersed: on thesupport layer (i.e., interfacial layer) surface, in crevices in thesupport layer, and in open pores in the support layer.

The catalyst may be supported on an assembly of one or more finspositioned within the process microchannels. Examples are illustrated inFIGS. 38-40. Referring to FIG. 38, fin assembly 380 includes fins 382which are mounted on fin support 384 which overlies base wall 386 ofprocess microchannel 388. The fins 382 project from the fin support 384into the interior of the process microchannel 388. The fins 382 extendto the interior surface of upper wall 390 of process microchannel 388.Fin channels 392 between the fins 392 provide passage ways for fluid toflow through the process microchannel 388 parallel to its length. Eachof the fins 382 has an exterior surface on each of its sides, thisexterior surface provides a support base for the catalyst. With theinventive process, the reactants flow through the fin channels 392,contact the catalyst supported on the exterior surface of the fins 382,and react to form the product. The fin assembly 380 a illustrated inFIG. 39 is similar to the fin assembly 380 illustrated in FIG. 38 exceptthat the fins 382 a do not extend all the way to the interior surface ofthe upper wall 390 of the microchannel 388. The fin assembly 380 billustrated in FIG. 40 is similar to the fin assembly 380 illustrated inFIG. 38 except that the fins 382 b in the fin assembly 380 b have crosssectional shapes in the form of trapezoids. Each of the fins (382, 382a, 382 b) may have a height ranging from about 0.02 mm up to the heightof the process microchannel 838, and in one embodiment from about 0.02to about 10 mm, and in one embodiment from about 0.02 to about 5 mm, andin one embodiment from about 0.02 to about 2 mm. The width of each fin(382, 382 a, 382 b) may range from about 0.02 to about 5 mm, and in oneembodiment from about 0.02 to about 2 mm and in one embodiment about0.02 to about 1 mm. The length of each fin (382, 382 a, 382 b) may be ofany length up to the length of the process microchannel 838, and in oneembodiment up to about 10 m, and in one embodiment about 1 cm to about10 m, and in one embodiment about 1 cm to about 5 m, and in oneembodiment about 1 cm to about 2.5 m. The gap between each of the fins(382, 382 a, 382 b) may be of any value and may range from about 0.02 toabout 5 mm, and in one embodiment from about 0.02 to about 2 mm, and inone embodiment from about 0.02 to about 1 mm. The number of fins (382,382 a, 382 b) in the process microchannel 388 may range from about 1 toabout 50 fins per centimeter of width of the process microchannel 388,and in one embodiment from about 1 to about 30 fins per centimeter, andin one embodiment from about 1 to about 10 fins per centimeter, and inone embodiment from about 1 to about 5 fins per centimeter, and in oneembodiment from about 1 to about 3 fins per centimeter. When viewedalong its length, each fin (382, 382 a, 382 b) may be straight, taperedor have a serpentine configuration. The fin assembly (380, 380 a, 380 b)may be made of any material that provides sufficient strength,dimensional stability and heat transfer characteristics to permitoperation for which the process microchannel is intended. Thesematerials include: steel (e.g., stainless steel, carbon steel, and thelike); monel; inconel; aluminum; titanium; nickel; platinum; rhodium;copper; chromium; brass; alloys of any of the foregoing metals; polymers(e.g., thermoset resins); ceramics; glass; composites comprising one ormore polymers (e.g., thermoset resins) and fiberglass; quartz; silicon;or a combination of two or more thereof. The fin assembly (380, 380 a,380 b) may be made of an Al₂O₃ forming material such as an alloycomprising Fe, Cr, Al and Y, or a Cr₂O₃ forming material such as analloy of Ni, Cr and Fe.

The catalyst may be supported by the microgrooved support stripillustrated in FIG. 41. Referring to FIG. 41, microgrooved support strip400 comprises support strip 410 which is rectangular in shape and has alength (l), width (w) and thickness (t). The support strip 410 has afirst or top surface 412, a second or bottom surface 414, a first sideedge 416, a second side edge 418, a front edge 420 and a back edge 422.The support strip 410 has a center axis 424 extending along the length(l) of the support strip. A plurality of parallel microgrooves 430 areformed in the first surface 412. The microgrooves 430 may extend betweenthe first side edge 416 of the support strip 410 and the second sideedge 418, but may not project through the side edges. The microgroovedsupport strip 400 includes non-grooved sections 434 and 436 whichprovide the microgrooved support strip 400 with a front edge 420 and aback edge 422 that are closed. That is, the front edge 420 and the backedge 422 of the microgrooved support strip 400 are sufficiently blockedto prevent fluid from flowing through the front edge 420 and back edge422. The microgrooves 430 may be oriented at an angle 425 relative tothe center axis 424 that is sufficient to permit fluid to flow in themicrogrooves 430 in a general direction from the front edge 420 towardthe back edge 422. The front edge 420, back edge 422 and side edges 416and 418 of the microgrooved support strip 400 are closed. These closededges do not permit the flow of fluid through the front edge, back edgeand side edges.

The microgrooves 430 illustrated in FIG. 41 have cross-sections in theform of squares. Alternatively, each of the microgrooves 430 may have arectangular cross-section, a vee shaped cross-section, a semi-circularcross-section, a dovetail shaped cross-section, or a trapezoid shapedcross-section. Those skilled in the art will recognize that microgrooveswith other cross-sectional shapes may be used. Each of the microgrooves430 has a depth, width and length. The depth of each of the microgrooves430 may be in the range from about 0.1 to about 1000 microns, and in oneembodiment from about 1 to about 100 microns. The width, which would bethe width at its widest dimension, for each of the microgrooves 430 maybe in the range of about 0.1 to about 1000 microns, and in oneembodiment from about 1 to about 500 microns. The length of each of themicrogrooves 430 may be of any dimension which depends upon the width(w) of the support strip 410. The length of each microgroove 430 may bein the range of about 0.1 to about 100 cm, and in one embodiment fromabout 0.1 to about 10 cm. The spacing between the microgrooves 430 maybe in the range up to about 1000 microns, and in one embodiment fromabout 0.1 to about 1000 microns, and in one embodiment from about 1 toabout 1000 microns. Each of the microgrooves 430 may be oriented towardthe back edge 422 and the first side edge 416 and forms an angle 425with the center axis 424 that may be sufficient to permit fluid to flowin the microgrooves in a general direction toward the second side edge418 and back edge 422. The angle 425 may be from about 0° to about 90°.The angle 425 may be in the range from about 50° to about 80°, and inone embodiment from about 60° to about 75°. The microgrooves 430 may bealigned at an angle of about 90° or at a right angle with the centeraxis 424, and in one embodiment extend from the first side edge 416 tothe second side edge 418. The microgrooves 430 may be aligned parallelto the center axis 424, and in one embodiment extend from the front edge420 to the back edge 422. The microgrooves 430 may be formed in thefirst surface 412 of the support strip 410 by any suitable technique,including photochemical machining, laser etching, water jet machining,and the like.

The support strip 410 may have a thickness (t) in the range from about0.1 to about 5000 microns, and in one embodiment from about 1 to about1000 microns. The support strip 410 may have any width (w) and anylength (l), the width and length depending upon the dimensions of themicrochannel for which the support strip 410 is to be used. The supportstrip 410 may have a width (w) in the range from about 0.01 to about 100cm, and in one embodiment from about 0.1 to about 10 cm. The length (l)of the support strip 410 may be in the range of about 0.01 to about 100cm, and in one embodiment from about 0.1 to about 10 cm. The supportstrip 410 as illustrated in FIG. 30 is in the form of a rectangle.However, it is to be understood that the support strip 410 may have anyconfiguration, for example, square, circle, oval, etc., to conform tothe design of the microchannel for which it is to be used.

The support strip 410 may be made of any material that providessufficient strength, dimensional stability and heat transfercharacteristics to permit the use of the microgrooved support strip 400in a microchannel for supporting a catalyst. The support strip 410 maybe made of metal, silicon carbide, graphite or a combination of two ormore thereof. The metal may comprise steel, aluminum, titanium, nickel,platinum, rhodium, copper, chromium, brass, or an alloy of any of theforegoing metals. The support structure 410 may be made of stainlesssteel or an alloy comprising iron, chromium, aluminum and yttrium.

The microgrooved support strip 400 may be used as a flow-by supportstructure in a microchannel.

In one embodiment, a plurality of the microgrooved support strips may bestacked one above another or positioned side by side to form a compositesupport structure which may be used to support a catalyst for use in theinventive process. The composite support structure, in one embodiment,is illustrated in FIGS. 44 and 45. The support strips 400A and 400Billustrated in FIGS. 44 and 45 have open front 420 and back edges 422,closed side edges 416 and 418, and microgrooves 430 that penetrate allthe way through the support strip 410 from the top surface 412 to thebottom surface 414. The open front edges 420, back edges 422 andmicrogrooves 430 permit fluid to flow through the microgrooved supportstrips from one support strip to another support strip within thecomposite support structure as the fluid flows through the compositesupport structure. The number of microgrooved support strips employed insuch a composite support structure may be of any number, for example upto about 50, and in one embodiment up to about 30, and in one embodimentup to about 15, and in one embodiment up to about 10. The compositesupport structure also includes end plates to prevent fluid from flowingout of the sides of the composite construction.

The composite support structure 402 illustrated in FIGS. 44 and 45comprises eight (8) microgrooved support strips, four each ofmicrogrooved support strips 400A and 400B positioned side by side inalternating sequence and two end plates 405 (only one end plate is shownin FIGS. 44 and 45). The microgrooved support strips 400A and 400B eachcomprise support strip 410 which is rectangular in shape and has alength, width and thickness. The support strip 410 has a center axisextending along the length of the support strip. A plurality of parallelmicrogrooves 430 are formed in the support strip 410 and project throughthe support strip from the top surface 412 to the bottom surface 414.The open front 420 and back edges 422 and the open microgrooves 430permit fluid to flow from one microgrooved support strip to anotherwithin the composite support structure 402. A first group of parallelmicrogrooves extends from the first side edge 416 of the support strip410 to the second side edge 418. A second group of the microgrooves 430extends from the front edge 420 to the second side edge 418. A thirdgroup of the microgrooves 430 extends from the first side edge 416 ofthe support strip 410 to the back edge 422. The microgrooves 430 extendto the side edges 416 and 418 but do not project through these sideedges. The end plates 405 prevent fluid from flowing out of the sides ofthe composite support structure 402. The second end plate 405 that isnot shown in the drawings would be positioned adjacent to the firstmicrogrooved support strip 400A on the left side in FIGS. 44 and 45. Themicrogrooves 430 in the support strips 400A may be oriented at an anglerelative to the center axis of the support strip and the side edge 416that is from about 90° to about 180°, and in one embodiment in the rangefrom about 100° to about 150°. The microgrooves 430 in the support strip400B may be oriented at an angle relative to the center axis of thesupport strip and the side edge 116 that is from about 0° to about 90°,and in one embodiment in the range from about 50° to about 80°. Fluidmay flow through the composite structure 402 by entering the front edge420 of the support strips 400A and 400B, flowing in and through themicrogrooves 430 and transferring from the microgrooves 430 in onesupport strip (400A or 400B) to the microgrooves 430 in another supportstrip (400A or 400B) until the fluid reaches the back edge 422 of thesupport strips and then flows out of composite support structure 402.FIG. 45 shows an example of a flow path through the composite supportstructure 402 for a fluid entering opening ‘A’ of the composite supportstructure illustrated in FIG. 44. The flow of fluid through thecomposite support structure 402 may be described as permeating,diffusing and advecting from one layer to another until the fluid passesfrom the front end of the composite support structure to the back end.

The catalyst may be deposited on the microgrooved support strips (400,400A, 400B) using conventional techniques. These may include washcoatingthe catalyst on the microgrooved support strips, growing the catalyst onthe microgrooved support strips, or depositing the catalyst on themicrogrooved support strips using vapor deposition. The vapor depositionmay be chemical vapor deposition or physical vapor deposition. Thecatalyst may be deposited by slurry-coating, sol-coating orsolution-coating. In one embodiment, the catalyst may be in the form ofmicrosized particulates deposited in and adhered to the microgrooves 430of the support strip or composite support structure. The catalystloading may be in the range from about 0.1 to about 100 milligrams (mg)per square centimeter of microgrooved support strip, and in oneembodiment in the range from about 1 to about 10 mg of catalyst persquare centimeter of microgrooved support strip. The microsizedparticulates may have average particle sizes in the range from about0.01 to about 100 microns, and in one embodiment in the range from about0.1 to about 50 microns, and in one embodiment in the range from about0.1 to about 10 microns, and in one embodiment from about 0.1 to about 7microns, and in one embodiment from about 0.1 to about 5 microns, and inone embodiment from about 0.1 to about 3 microns, and in one embodimentfrom about 0.1 to about 2 microns, and in one embodiment from about 0.1to about 1 micron, and in one embodiment from about 0.1 to about 0.5micron.

An advantage of the microgrooved support strips and composite structuresrelates to the fact that microsized particles of catalyst may bepositioned in and anchored to the microgrooves thus reducing thetendency of the particulates being swept away by the flow of processfluids through the microchannels.

Repeating units 200W and 200X for use in microchannel processing unitcore 102 employing microgrooved support strip 400 for supporting acatalyst are illustrated in FIGS. 42 and 43. The number of theserepeating units that may be used in the microchannel processing unitcore 102 may be any number, for example, one, two, three, four, five,six, eight, ten, hundreds, thousands, etc. Referring to FIG. 42,repeating unit 200W includes process microchannel 210 with microgroovedsupport strip 400 mounted on interior wall 230 of the processmicrochannel 210. Bulk flow region 234 is the space within the processmicrochannel 210 above the microgrooved support strip 400. Process fluidflows through the process microchannel 210 as indicated by arrows 215and 216. In flowing through the process microchannel 210, the processfluid flows through the bulk flow region 234 in contact with thecatalyst supporting microgrooved support strip 400. The catalyst may bein the form of microsized particulates positioned in the microgrooves430. The microgrooved support strip 400 is a flow-by support strip.However, some of the process fluid may flow in the microgrooves 430 incontact with the catalyst. The flow of the process fluid through themicrogrooves 430 may be in the general direction from the side edge 418toward the side edge 416 and the back edge 422. Heat exchange channels(not shown in the drawing) may be provided for heating and/or coolingthe process microchannel 210.

The repeating unit 200X illustrated in FIG. 43 is similar to therepeating unit 200W illustrated in FIG. 42 with the exception that theprocess microchannel 210 illustrated in FIG. 43 contains oppositeinterior walls 230 and 232 and a catalyst supporting microgroovedsupport strip 400 mounted on each of the opposite interior walls.

An advantage of the inventive process, at least in one embodiment, isthat the gap distances between the process microchannels, stagedaddition channels, and heat exchange channels may be the same whetherthe process is intended for laboratory or pilot plant scale or for fullproduction scale. As a result, the particle size distribution of thesecond fluid in the multiphase fluid mixtures produced by themicrochannel processing units used with the inventive process may besubstantially the same whether the microchannel processing unit is builton a laboratory or pilot plant scale or as a full scale plant unit.

Shear force or stress on a liquid control element (in discretized form)in the direction of velocity u may be calculated by the formulaF_(x)=mu*du/dy, where mu is viscosity, and du/dy is the velocitygradient for the liquid flow normal to the apertured section. However,as in a location of fluid (represented by a control element) thevelocity generally has three components, and shear force also has threecomponents. For a channel flow near and at the surface, a onedimensional assumption can be made and F_(x) can approximate the netshear stress at an element surface of the liquid. The use ofcomputational fluid dynamics, including commercial software packagessuch as Fluent or FEMLAB, may be used to solve the required transportequations such that the surface shear force may be calculated. Thesurface shear force or stress may be calculated along the channellength, parallel to the direction of flow. Shear force or stress mayalso be calculated between parallel channels, where flow distributioneffects are included to determine the mass flux into each parallelchannel as a function of the detailed channel and manifold geometry.Additional calculation methods can be found, for example, in“Fundamentals of Fluid Mechanics,” 3^(rd) Ed., B. R. Munson, D. F. Youngand T. H. Okiishi, John Wiley & Son, Inc., Weinheim, 1998.

In one embodiment, the shear force deviation factor (SFDF) for a processemploying a single process microchannel may be within about 50% of theSFDF for a scaled-up process involving multiple process microchannels.SFDF may be calculated using the formula

SFDF=(F _(max) −F _(min))/(2F _(mean))

wherein: F_(max) is the maximum shear stress force in a processmicrochannel for a specific liquid; F_(min) is the minimum shear stressforce in the process microchannel for the liquid; and F_(mean) is thearithmetic average shear force for the fluid at the surface of theapertured section (250, 250A) within the process microchannel 210.Within a single process microchannel, operated in accordance with theinventive process, the SFDF may be less than about 2, and in oneembodiment less than about 1, and in one embodiment less than about 0.5,and in one embodiment less than about 0.2.

In one embodiment, the inventive process may provide for a relativelyuniform shear stress force while employing multiple processmicrochannels. To measure the shear force uniformity among multipleprocess microchannels, the average shear force is calculated for eachchannel and compared. F_(max) is the largest value of the averagechannel shear force, and F_(min) is the smallest value of the averageshear force. F_(mean) is the mean of the average shear forces of all thechannels. SFDF may be calculated from these values. Among multipleprocess microchannels, at least with one embodiment of the inventiveprocess, the SFDF may be less than about 2, and in one embodiment lessthan about 1, and in one embodiment less than about 0.5, and in oneembodiment less than about 0.2.

The deviation in the shear force within a process microchannel may alsobe defined as:

${SFDF}^{\prime} = \frac{F_{\max} - F_{\min}}{F_{\max}}$

wherein F_(max), F_(min) are as defined above. In one embodiment, theSFDF′ may be less than about 0.9, and in one embodiment less than about0.5, and in one embodiment less than about 0.1.

For a multiple process channel, the deviation in shear force may bedefined as:

${SFDF}^{''} = \frac{F_{\max}^{\prime} - F_{\min}^{\prime}}{F_{\max}^{\prime}}$

wherein F′_(max) is defined as the maximum shear force at a given axiallocation for multiple process microchannels, and F′_(min) is defined asthe minimum shear force at the same axial location for the multipleprocess microchannels. In one embodiment, the SFDF″ may be less thanabout 0.9, and in one embodiment less than about 0.5, and in oneembodiment less than about 0.1.

In a scale up device, for certain applications, it may be required thatthe mass of the process fluid be distributed uniformly among themicrochannels. Such an application may be when the process fluid isrequired to be heated or cooled down with adjacent heat exchangechannels. The uniform mass flow distribution may be obtained by changingthe cross-sectional area from one parallel microchannel to anothermicrochannel. The uniformity of mass flow distribution may be defined byQuality Index Factor (Q-factor) as indicated below. A Q-factor of 0%means absolute uniform distribution.

$Q = {\frac{{\overset{.}{m}}_{\max} - {\overset{.}{m}}_{\min}}{{\overset{.}{m}}_{\max}} \times 100}$

A change in the cross-sectional area may result in a difference in shearstress on the wall.

In one embodiment, the Q-factor for the process microchannels may beless than about 50%, and in one embodiment less than about 20%, and inone embodiment less than about 5%, and in one embodiment less than about1%.

In one embodiment, the Q-factor for the process microchannel may be lessthan about 50% and the SFDF″ may be less than about 0.8. In oneembodiment, the Q-factor may be less than about 5%, and the SFDF″ lessthan about 0.5. In one embodiment, the Q-factor may be less than about1%, and the SFDF″ may be less than about 0.1.

A heat source and/or heat sink may be used for cooling, heating or bothcooling and heating. The heat source and/or heat sink may comprise oneor more heat exchange channels. The heat source may comprise one or morenon-fluid heating elements such as one or more electric heating elementsor resistance heaters. The heat sink may comprise one or more non-fluidcooling elements. These may be adjacent to the process microchannelsand/or staged addition channels. In one embodiment, the heat sourceand/or heat sink may not be in contact with or adjacent to the processmicrochannel and/or staged addition channels, but rather can be remotefrom either or both the process microchannel and/or staged additionchannels, but sufficiently close to the process microchannel and/orstaged addition channels to transfer heat between the heat source and/orheat sink and the process microchannels and/or staged addition channels.The non-fluid heating and/or non-fluid cooling elements may be used toform one or more walls of the process microchannels (210) and/or stagedaddition channels (240, 240A). The non-fluid heating and/or coolingelements may be built into one or more walls of the processmicrochannels and/or staged addition channels. The non-fluid heatingand/or cooling elements may be thin sheets, rods, wires, discs orstructures of other shapes embedded in the walls of the processmicrochannels and/or staged addition channels. The non-fluid heatingand/or cooling elements may be in the form of foil or wire adhered tothe process microchannel walls and/or staged addition channel walls.Heating and/or cooling may be effected using Peltier-type thermoelectriccooling and/or heating elements. Multiple heating and/or cooling zonesmay be employed along the length of the process microchannels and/orstaged addition channels. Similarly, heat transfer fluids at differenttemperatures in one or more heat exchange channels may be employed alongthe length of the process microchannels and/or staged addition channels.The heat source and/or heat sink may be used to provide precisetemperature control within the process microchannels and/or stagedaddition channels.

The heat exchange fluid may be any fluid. These include air, steam,liquid water, gaseous nitrogen, liquid nitrogen, other gases includinginert gases, carbon monoxide, carbon dioxide, oils such as mineral oil,gaseous hydrocarbons, liquid hydrocarbons, and heat exchange fluids suchas Dowtherm A and Therminol which are available from Dow-Union Carbide.

The heat exchange fluid may comprise the first fluid, second fluidand/or product. This can provide process pre-heat and/or an increase inoverall thermal efficiency of the process.

In one embodiment, the heat exchange channels comprise process channelswherein an endothermic or exothermic process is conducted. These heatexchange process channels may be microchannels. Examples of endothermicprocesses that may be conducted in the heat exchange channels includesteam reforming and dehydrogenation reactions. Examples of exothermicprocesses that may be conducted in the heat exchange channels includewater-gas shift reactions, methanol synthesis reactions and ammoniasynthesis reactions.

In one embodiment, the heat exchange fluid undergoes a phase change inthe heat exchange channels. This phase change provides additional heataddition to or removal from the process microchannels and/or secondreactant stream channels beyond that provided by convective heating orcooling. An example of such a phase change would be an oil or water thatundergoes boiling. In one embodiment, the vapor mass fraction quantityof the boiling of the phase change fluid may be up to about 100%, and inone embodiment up to about 75%, and in one embodiment up to about 50%.

The heat flux for heat exchange in the microchannel processing unit maybe in the range from about 0.01 to about 500 watts per square centimeterof surface area of the heat transfer walls in the microchannelprocessing unit (W/cm²), and in one embodiment from about 0.1 to about250 W/cm², and in one embodiment from about 0.1 to about 100 W/cm², andin one embodiment from about 1 to about 100 W/cm², and in one embodimentfrom about 1 to about 50 W/cm², and in one embodiment from about 1 toabout 25 W/cm², and in one embodiment from about 1 to about 10 W/cm².

In one embodiment, the temperature of the fluid streams entering themicrochannel processing unit 100 may be within about 200° C., and in oneembodiment within about 100° C., and in one embodiment within about 50°C., and in one embodiment within about 20° C., of the temperature of theproduct exiting the microchannel processing unit 100.

The use of controlled heat exchange between heat exchange channels inclose proximity or adjacent to the process microchannels and/or stagedaddition channels may allow for uniform temperature profiles for theprocess microchannels and/or staged addition channels. This provides forthe possibility of a more uniform heat exchange at more rapid rates thancan be obtained with conventional processing equipment such as mixingtanks. For a microchannel processing unit employing multiple processmicrochannels and optionally multiple staged addition second channels,the temperature difference between the process microchannels and/orstaged addition channels at least one common position along the lengthsof the process microchannels may be less than about 5° C., and in oneembodiment less than about 2° C., and in one embodiment less than about1° C.

The heat exchange zones 270 adjacent to either the process microchannelsand/or staged addition channels may employ separate temperature zonesalong the length of such channels. For example, in one embodiment, thetemperature in a first zone near the entrance to the processmicrochannel may be maintained at a temperature above or below a secondtemperature in a second zone near the end of the process microchannel. Acool down or quench zone may be incorporated into the processmicrochannels to cool the product. Numerous combinations of thermalprofiles are possible, allowing for a tailored thermal profile along thelength of the process microchannels and/or staged addition channels,including the possibility of heating or cooling zones before and/orafter the reaction zone in the process microchannels to heat or cool thereactants and/or product.

The heat exchange fluid entering the heat exchange channels may be at atemperature in the range from about −40° C. to about 400° C., and in oneembodiment about 0° C. to about 400° C., and in one embodiment fromabout 20° C. to about 300° C., and in one embodiment from about 20° C.to about 250° C., and in one embodiment from about 20° C. to about 200°C. The heat exchange fluid exiting the heat exchange channels may be ata temperature in the range from about −40° C. to about 400° C., and inone embodiment about 0° C. to about 400° C., and in one embodiment fromabout 20° C. to about 300° C., and in one embodiment from about 20° C.to about 250° C., and in one embodiment from about 20° C. to about 200°C. The residence time of the heat exchange fluid in the heat exchangechannels may be in the range from about 5 ms to about 1 minute, and inone embodiment from about 20 ms to about 1 minute, and in one embodimentfrom about 50 ms to about 1 minute, and in one embodiment about 100 msto about 1 minute. The pressure drop for the heat exchange fluid as itflows through the heat exchange channels may be in the range up to about1 atm/m, and in one embodiment up to about 0.5 atm/m, and in oneembodiment up to about 0.1 atm/m, and in one embodiment from about 0.01to about 1 atm/m. The heat exchange fluid may be in the form of a vapor,a liquid, or a mixture of vapor and liquid. The Reynolds Number for theflow of vapor through the heat exchange channels may be in the rangefrom about 10 to about 5000, and in one embodiment about 100 to about3000. The Reynolds Number for the flow of liquid through heat exchangechannels may be in the range from about 10 to about 10000, and in oneembodiment about 100 to about 5000.

The design of the process microchannels may vary along their axiallength to accommodate the changing hydrodynamics within the processmicrochannels. For example, if one of the reactants is in excess, thenthe fluidic properties of a reaction mixture may change over the courseof the reaction as typified by an extent of reaction less than about 10%to an extent of reaction greater than about 50%. For an oxidationreaction where oxygen is fed near the stoichiometric feed rate, at theentrance to the process microchannel the ratio of liquid to gas may bemodest, but at the end of the process microchannel the ratio of liquidto gas may be high and approach infinity for reactions that are desiredto go to extinction of the gas reactant. Reduction of mass transferrequires good phase mixing. Good phase mixing may require a differentdesign as the gas or alternatively the liquid are reacted to nearcompletion, for example, greater than about 60% conversion, and in oneembodiment greater than about 90% conversion. There may be at least onesecond reaction zone in the process microchannel in which themicrochannel cross section is reduced or increased from that in thecorresponding first reaction zone to create a different mixing pattern.Surface features, if used, may have a different geometry, pattern,angle, depth, or ratio of size relative to the microchannel gap as thereaction proceeds toward extinction.

In one embodiment of the invention relatively short contact times, highselectivity to the desired product and relatively low rates ofdeactivation of the catalyst may be achieved by limiting the diffusionpath required for the catalyst. For example, this may be achieved whenthe catalyst is in the form of a thin layer on an engineered supportsuch as a metallic foam or on the wall of the process microchannel. Thisallows for increased space velocities. In one embodiment, the thin layerof catalyst can be produced using chemical vapor deposition. This thinlayer may have a thickness in the range up to about 1 micron, and in oneembodiment from about 0.1 to about 1 micron, and in one embodiment about0.25 micron. These thin layers may reduce the time the reactants arewithin the active catalyst structure by reducing the diffusional path.This decreases the time the reactants spend in the active portion of thecatalyst. The result may be increased selectivity to the product andreduced unwanted by-products. An advantage of this mode of catalystdeployment is that, unlike conventional catalysts in which the activeportion of the catalyst may be bound up in an inert low thermalconductivity binder, the active catalyst film is in intimate contactwith either the engineered structure or the wall of the processmicrochannel. This may leverage high heat transfer rates attainable inthe microchannel reactor and allows for close control of temperature.The result is the ability to operate at increased temperature (fasterkinetics) without promoting the formation of undesired by-products, thusproducing higher productivity and yield and prolonging catalyst life.

In one embodiment, the catalyst may be regenerated. This may be done byflowing a regenerating fluid through the process microchannels 210 incontact with the catalyst. The regenerating fluid may comprise hydrogenor a diluted hydrogen stream. The diluent may comprise nitrogen, argon,steam, methane, carbon dioxide, or a mixture of two or more thereof. Theconcentration of H₂ in the regenerating fluid may range up to about 100%by volume, and in one embodiment from about 1 to about 100% by volume,and in one embodiment about 1 to about 50% volume. The regeneratingfluid may flow from the header 104 through the process microchannels tothe footer 106, or in the opposite direction from the footer 106 throughthe process microchannels to the header 104. The temperature of theregenerating fluid may be from about 20 to about 600° C., and in oneembodiment about 20 to about 400° C., and in one embodiment about 80 toabout 200° C. The pressure within the process microchannels 210 duringthis regeneration step may range from about 1 to about 100 atmospheresabsolute pressure, and in one embodiment about 1 to about 10atmospheres. The residence time for the regenerating fluid in theprocess microchannels may range from about 0.001 to about 10 seconds,and in one embodiment about 0.01 second to about 1 second.

The contact time of the reactants and product with the catalyst withinthe process microchannels 210 may be in the range up to about 100seconds, and in one embodiment in the range from about 1 millisecond(ms) to about 100 seconds, and in one embodiment in the range from about1 ms to about 50 seconds, and in one embodiment in the range from about1 ms to about 25 seconds, and in one embodiment in the range from about1 ms to about 10 seconds, and in one embodiment from about 1 ms to about1 second, and in one embodiment from about 1 ms to about 500 ms, and inone embodiment about 1 ms to about 200 ms, and in one embodiment about 1ms to about 100 ms, and in one embodiment about 1 ms to about 50 ms, andin one embodiment about 1 ms to about 20 ms, and in one embodiment about1 ms to about 10 ms.

The flow rate of fluid flowing in the process microchannels 210 may bein the range from about 0.001 to about 500 lpm, and in one embodimentabout 0.001 to about 250 lpm, and in one embodiment about 0.001 to about100 lpm, and in one embodiment about 0.001 to about 50 lpm, and in oneembodiment about 0.001 to about 25 lpm, and in one embodiment about 0.01to about 10 lpm. The velocity of fluid flowing in the processmicrochannels may be in the range from about 0.01 to about 200 m/s, andin one embodiment about 0.01 to about 75 m/s, and in one embodimentabout 0.01 to about 50 m/s, and in one embodiment about 0.01 to about 30m/s, and in one embodiment about 0.02 to about 20 m/s. The ReynoldsNumber for the fluid flowing in the process microchannels may be in therange from about 0.0001 to about 100000, and in one embodiment about0.001 to about 10000.

The weight hourly space velocity (WHSV) for the flow of the reactantsand product in the process microchannels may be at least about 0.1 (mlfeed)/(g catalyst)(hr). The WHSV may range from about 0.1 to about 5000,and in one embodiment, the WHSV may range from about 1 to about 500 (mlfeed)/(g catalyst)(hr), and in one embodiment the WHSV may be in therange from about 10 to about 500 (ml feed)/(g catalyst)(hr).

The residence time for the flow of fluids in the process microchannelsmay be in the range from about 0.005 to about 100 seconds, and in oneembodiment from about 0.03 to about 10 seconds.

While not wishing to be bound by theory, it is believed that a highsuperficial velocity in the process microchannels 210 may beadvantageous for reactions wherein both gas and liquid phases arepresent during the reaction. This is because the shear stress force ofthe fluid may act to thin liquid layers that typically form on thesurface of the catalyst. Thinner liquid film layers may reduce the masstransfer resistance of the reactants to the catalyst surface and improveconversion at relatively short contact times for the reactants, forexample, contact times less than about 500 milliseconds. In oneembodiment, the superficial velocity for the fluids flowing through theprocess microchannels may be at least about 0.01 meters per second(m/s), and in one embodiment in the range from about 0.01 to about 50m/s, and in one embodiment in the range from about 0.01 to about 10 m/s,and in one embodiment in the range from about 0.01 to about 1 m/s, andin one embodiment in the range from about 0.05 to about 0.5 m/s.

The temperature of the fluids entering the microchannel processing unit100 or processing unit core 102 may be in the range from about −40° C.to about 400° C., and in one embodiment about 0° C. to about 400° C.,and in one embodiment from about 20° C. to about 300° C., and in oneembodiment from about 20° C. to about 250° C., and in one embodimentfrom about 20° C. to about 200° C.

The temperature within the process microchannels 210 may be in the rangefrom about −40° C. to about 400° C., and in one embodiment from about 0°C. to about 400° C., and in one embodiment from about 20° C. to about300° C., and in one embodiment from about 20° C. to about 250° C., andin one embodiment from about 20° C. to about 200° C.

The temperature of the product exiting the microchannel processing unit100 or processing unit 102 may be in the range from about −40° C. toabout 400° C., and in one embodiment about 0° C. to about 400° C., andin one embodiment from about 20° C. to about 300° C., and in oneembodiment from about 20° C. to about 250° C., and in one embodimentfrom about 20° C. to about 200° C.

The pressure within the process microchannels 210 may be in the range upto about 50 atmospheres absolute pressure, and in one embodiment up toabout 40 atmospheres, and in one embodiment up to about 30 atmospheres.In one embodiment the pressure may be in the range from about 1 to about50 atmospheres absolute pressure, and in one embodiment from about 10 toabout 40 atmospheres, and in one embodiment from about 20 to about 30atmospheres.

The pressure drop of the reactants and/or products as they flow in theprocess microchannels 210 may be in the range up to about 1 atmosphereper meter of length of the process microchannel (atm/m), and in oneembodiment up to about 0.5 atm/m, and in one embodiment up to about 0.1atm/m.

The pressure drop for the second fluid flowing through the aperturedsections (250, 250A) may be in the range up to about 0.1 atm, and in oneembodiment from about 0.001 to about 0.1 atm, and in one embodiment fromabout 0.001 to about 0.05 atm, and in one embodiment about 0.001 toabout 0.005 atm. Reactants or products flowing in the processmicrochannels 210 may be in the form of a vapor, a liquid, or a mixtureof vapor and liquid. The Reynolds Number for the flow of vapor in theprocess microchannels may be in the range from about 10 to about 10000,and in one embodiment about 100 to about 3000. The Reynolds Number forthe flow of liquid in the process microchannels may be about 10 to about10000, and in one embodiment about 100 to about 3000.

The conversion of the first reactant may be in the range from about 5%or higher per cycle, and in one embodiment from about 15 to about 100%.

The conversion of the second reactant may be in the range from about 25%or higher per cycle, and in one embodiment from about 25 to about 100%per cycle.

The yield of product may be in the range from about 20% or higher percycle, and in one embodiment from about 20 to about 50% per cycle.

Emulsion formation within microchannels enables smaller mean dropletsizes for new commercial applications such as personal care, medical,and food products among others. When operated at a high flow rate perchannel, the resulting emulsion mixture creates a high wall shear stressalong the walls of the narrow microchannel. This high fluid-wall shearstress of continuous phase material past a dispersed phase, introducedthrough a permeable wall, enables the formation of small emulsiondroplets—one drop at a time. These emulsions may be referred to asnon-Newtonian fluids. A problem with the scale-up of this technology hasbeen to understand the behavior of non-Newtonian fluids under high wallshear stress. A further complication has been the change in fluidproperties with composition along the length of the microchannel as theemulsion is formed.

Many of the predictive models for non-Newtonian emulsion fluids arederived at low shear rates and have shown excellent agreement betweenpredictions and experiments. The power law relationship fornon-Newtonian emulsions obtained at low shear rates breaks down underthe high shear environment created by high throughputs in smallmicrochannels. The small dimensions create higher velocity gradients atthe wall, resulting in larger apparent viscosity. Extrapolation of thepower law obtained in low shear environments may not accurately predictpressure drops that may occur in microchannels at high flow rates.

The results for a shear-thinning fluid that generates larger pressuredrops in a high-wall shear stress microchannel environment predictedfrom traditional correlations are described below. The followingnomenclature is used:

f=fanning friction factor

D=hydraulic diameter of channel, m

k=power law constant

L=length of channel, m

n=power law coefficient

R=radius of the channel, m

Re=Reynolds number

V=average velocity of fluid in channel, m/s

x⁺=dimensionless developing length

ΔP=pressure drop, Pa

ρ=density of fluid in channel, kg/m³

μ=viscosity, kg/m-s

τ=shear stress, N/m²

γ=shear rate, sec⁻¹

Emulsions may be referred to as dispersions containing a component thatinfluences fluid-fluid interface stabilization. In many cases, thecomponents of these emulsions as well as the emulsions do not follow theNewtonian relationship between shear stress and shear rate. Therelationship between shear stress and shear rate plays an important rolein predicting flow dynamics of non-Newtonian fluids as well as designparameters (e.g., pressure drop) for microchannel processing units.

When predicting pressure drop for a non-Newtonian fluid in a macro-scalepipe, rheological parameters such as the power law constants are used inconjunction with established theoretical or empirical correlations forvelocity profile. Rheological parameters for velocity profile are oftenobtained from a benchtop rheometer or laboratory viscometer. However,because there are no well established correlations for velocity profilefor a non-Newtonian fluid in a microchannel, translation of rheologicalparameters from a rheogram to a high shear environment and ultimatelypressure drop can be inaccurate for small dimension systems.

Instead of using a rheogram as the basis for design calculations, it maybe experimentally more convenient and accurate to use a pipelineviscometer (a form of a capillary viscometer) to measure rheologicalparameters for the high shear environment created in microchannels. Theapplicability of shear stress and shear rate relationship for shearthinning non-Newtonian fluid in microchannel environment is describedbelow.

Most of the applications in the industry are limited by allowablepressure drop. The purpose of flow modeling is to understand and obtainthe pressure drop in the system and parameters affecting it. Thissection describes equations that may be used for pressure dropestimation in straight conduits.

Newtonian Fluid

For Newtonian fluids, the shear stress changes proportional to shearrate. The constant of proportionality is called dynamic viscosity and isconstant for a given fluid at constant temperature and pressure.

τ=μγ  (1)

Based on the above stress and strain relationship, the general form ofpressure drop equation in a straight conduit with Newtonian fluid isgiven by:

$\begin{matrix}{{\Delta \; P} = {4f\frac{L}{D}\frac{\rho \; V^{2}}{2}}} & (2)\end{matrix}$

Where the fanning friction factor (f) is a dimensionless number andrepresents the shear stress on the channel wall. The value of thefriction factor depends on the flow regime (or Reynolds number), conduitgeometry and wall surface roughness. The fanning friction factor for acircular channel geometry is dependent on the Reynolds number and islisted below.Laminar Regime (Re<2200): The friction factor in laminar regime isdependent on dimensionless developing length and may be estimated by:

$\begin{matrix}{{f = \frac{\left( \frac{3.44}{\left\lbrack x^{+} \right\rbrack^{0.5}} \right) + \frac{\left( \frac{1.25}{{4\left\lbrack x^{+} \right\rbrack}^{0.5}} \right) + 16 - \left( \frac{3.44}{\left\lbrack x^{+} \right\rbrack^{- 0.5}} \right)}{1 + {0.00021\left( x^{+} \right)^{- 2}}}}{Re}};{{{For}\mspace{14mu} x^{+}} \leq 0.1}} & (3) \\{{f = \frac{16}{Re}};{{{For}\mspace{14mu} x^{+}} > 0.1}} & (4)\end{matrix}$

Transition Regime (2200≦Re<4000): The friction factor in a circularchannel for the transition regime may be given by:

$\begin{matrix}{f = {0.00128 + \frac{0.1143}{{Re}^{\frac{1}{3.2154}}}}} & (5)\end{matrix}$

Turbulent Regime (Re≧4000): The friction factor in circular channel fortransition regime may be given by:

$\begin{matrix}{f = {0.0054 + \frac{2.3 \times 10^{- 8}}{{Re}^{- 1.5}}}} & (6)\end{matrix}$

The Reynolds number and dimensionless length may be given by

$\begin{matrix}{{Re} = \frac{\rho \; {VD}}{\mu}} & (7) \\{x^{+} = \frac{L}{D\; {Re}}} & (8)\end{matrix}$

Non-Newtonian Fluid

For a shear-thinning non-Newtonian fluid the traditional relationshipbetween shear stress and shear rate is shown in FIG. 52. The regionswhere the shear stress (or viscosity) does not change with shear ratemay be referred to as Newtonian regions. The behavior between theseregions may be a straight line on a log-log scale, and may be known as apower-law region.

The behavior of fluid in the power law region may be approximated by:

μ=kγ ^(n-1)  (9)

The fully developed velocity profile and shear rate for shear-thinningfluid obeying power law in laminar flow regime in a circular conduit maybe given by:

$\begin{matrix}{\frac{V}{\overset{\_}{V}} = {\frac{{3n} + 1}{n + 1}\left( {1 - \left( \frac{r}{R} \right)^{\frac{n + 1}{n}}} \right)}} & (10) \\{\gamma = {{\overset{\_}{V}\left( \frac{{3n} + 1}{n} \right)}\frac{r^{n}}{R^{\frac{n + 1}{n}}}}} & (11)\end{matrix}$

Generally, a mathematical problem involving a non-Newtonian fluidinvolves solving the Navier-Strokes equation. However, if the values ofk and n can be determined by a viscometer, a simple method to estimatepressure drop with a non-Newtonian fluid can be developed by using powerlaw relationships as described in equations (9), (10), (11) inconjunction with (2) to (4). This method of pressure drop estimation maybe referred to as the 1-D method.

A test device for experimentally measuring the viscosity in a high shearrate environment is illustrated in FIG. 53. A stainless steel tube witha circular cross-section is used. The nominal tube diameter is 1.59 mm.The nominal thickness of the tube wall is 0.43 mm. The length of thetube is 610 mm. The test apparatus is prepared by cutting the requiredlength of tubing from the coil stock and removing the burrs at both endsof the tube using a de-burrer.

Fluid is fed by a syringe pump, Isco model 260D. The pump is accurate to0.001 ml/min. The maximum delivery pressure for the pump is 20,800 kPa(205.3 atmospheres). The pressure of the liquid, at the inlet and theoutlet of the test apparatus, is measured using pressuretransducers-NOSHOK Series 100. A single pressure transducer is used atthe outlet of the test apparatus with range from 0 to 136 kPa (5 psig,1.34 atmospheres). At the inlet of the test device, two pressuretransducers are used. One transducer has range from 0 to 791 kPa (100psig, 7.81 atmospheres), while the other pressure transducer has rangefrom 0 to 7000 kPa (1000 psig, 69.1 atmospheres). When the inletpressure is less than 710 kPa (7.01 atmospheres), the pressuretransducer with range from 0 to 791 kPa (7.81 atmospheres) is usedotherwise the pressure transducer with range 0 to 7000 kPa (69.1atmospheres) is used. The accuracy of the pressure transducers is ±0.5%of the pressure range. The outlet of the test device is kept at ambientpressure conditions. The inlet and the outlet temperature of the fluidto the test apparatus is measured using Omega Type K thermocouples withaccuracy of ±2° C. The entire test device is kept at ambient temperatureconditions. Any viscous heat generation is dissipated to the ambient.

The connections to the test device are made using graphite ferrules andswagelok fittings to prevent compression of the tube at the ends.

The temperature and pressure data are electronically recorded usingNational Instruments Labview 7.1. The interval of data recording is 1second.

Prior to performing any experiments, the pressure transducers arecalibrated for accurate pressure measurement. The standard used forcalibration is Fluke 725 w/700PO7 pressure module. The calibration curveis built by comparing raw pressure transducer output current (in mA)read by the data logging Labview software against the pressure measuredby Fluke725 equipped with a pressure module (in kPa). The pressure isintroduced using Altech 368-600 high pressure hand pump. Minimum sixpoints are used to generate the calibration curves. The relationsbetween the applied pressure and pressure transducer signal are found tobe linear for all three pressure transducers. The calibration curves arethen used for pressure measurements during the experiments. FIG. 54shows the calibration curve for 136 kPa (1.34 atmospheres), 791 kPa(7.81 atmospheres) and 7000 kPa (69.1 atmospheres) range pressuretransducers.

The accuracy of the pump is measured to be within ±0.5%.

An experimental test plan is developed to estimate pressure drop forboth a Newtonian and a non-Newtonian fluid. The Newtonian fluid that isused is de-ionized water. The non-Newtonian fluid is prepared usingrheology modifier dissolved in de-ionized water. The rheology modifierused is Carbopol SF-1 from Noveon. The experimental test plan is shownin Table 1.

TABLE 1 Experimental test plan for Newtonian and non-Newtonian fluidsOutlet Test Run Flow rate pressure Temperature number (ml/min) (kPa) (°C.) 1 10.0 Ambient Ambient 2 21.3 Ambient Ambient 3 32.5 Ambient Ambient4 43.8 Ambient Ambient 5 55.0 Ambient Ambient 6 77.5 Ambient Ambient 788.8 Ambient Ambient 8 100.0 Ambient Ambient

Deionized water is used as the Newtonian fluid. The de-ionized water isprepared by using a deionizer manufactured by Elga, model Medica 17R.The setting is at 18MΩ.

Three non-Newtonian solutions are prepared using the Noveon Carbopolpolymer. Carbopol polymers are high molecular weight homo- andcopolymers of acrylic acid crosslinked with a polyalkenyl polyether.When used at concentrations lower than 1%, these polymers offer a widerange of rheological properties. The first solution is prepared bymixing 4.2 g of Carbopol polymer in 500 g of de-ionized water. Thesecond solution is made by mixing 5.6 g of Carbopol polymer in 500 g ofde-ionized water. The third solution is made by mixing 8.4 g of Carbopolpolymer in 500 g of de-ionized water. All the solutions are brought topH 6.8-7.2 by dropwise addition of 0.1N NaOH, stirring while the pH ismonitored. The first solution is referred as low viscosity, the secondsolution is referred as medium viscosity while the third solution isreferred as high viscosity. Each of these are non-Newtonian fluids.

The viscosity of non-Newtonian fluids is measured using BrookfieldRVDV-E viscometer equipped with a UL adapter. The spindle used forviscosity measurement is ULA-000.

FIG. 55 shows the measured viscosity of the Carbopol solution as afunction of shear rate for low, medium and high viscosity non-Newtonianfluids as tested by a Brookfield viscometer.

The linear relationship between viscosity and shear rate on a log-logscale indicates that the fluid is a shear-thinning non-Newtonian fluidfollowing a traditional power law relationship.

The reservoir of the pump is filled with the testing fluid. The datarecording is started to electronically record the pressures andtemperatures. The required flow rate to the test device is set in thesyringe pump and the syringe pump is started. The flow is consideredsteady-state when the fluctuation in the inlet pressure transducer isless than 3.5 kPa (0.035 atmosphere). The steady state is maintained for30 to 60 seconds to collect inlet and outlet pressure and temperatureinformation. After all the test runs for a fluid are completed, thesystem is purged by pumping 50 ml of air, flushed with 20 ml of the nextfluid before beginning the tests. Several run points are repeated tovalidate the reproducibility. The pressure drop across the test deviceis calculated by difference of inlet and outlet measured pressures.

FIG. 56 shows the comparison of experimental pressure drop withpredictions for water. Equations (2) through (8) are used for thepredictions of pressure drop. As shown in FIG. 56, there is an excellentagreement between measured pressure drop and predicted pressure drop forwater as a Newtonian fluid. The comparison validates the selectedfriction factor correlations.

The viscosity measurements made by a Brookfield viscometer, as shown inFIG. 55, are used to calculate constants k and n in the power lawrelationship between viscosity and shear rate. The values of k and n forlow, medium and high viscosity non-Newtonian fluid are summarized inTable 2.

TABLE 2 Summary of k and n values for non-Newtonian fluid fromBrookfield viscometer k N Low Viscosity 0.16 0.65 Medium Viscosity 0.550.49 High Viscosity 2.13 0.33

Using the equations (2), (9-11) and values of k and n in Table 2,pressure drop is predicted for low, medium and high viscositynon-Newtonian fluid in the test device. FIGS. 57-59 compare theexperimental pressure drop and the predicted pressure drop for low,medium and high viscosity non-Newtonian fluids. In all the cases, theexperimental pressure drop is larger than the pressure drop predicted bythe 1-D method that is based on the fit of the power law coefficientsobtained in the low shear Brookfield viscometer.

Computation fluid dynamics method is also used to validate the 1-Dmethod. A simple mesh of the test device is developed in Gambit. Thesoftware used for computation fluid dynamics is Fluent V6.2.16. Thepower law coefficients obtained from Brookfield Viscometer, as listed inTable 2, are used in the analysis. A good agreement is observed betweenthe predictions from the computation fluid dynamics method and the 1-Dmethod as shown in FIG. 58.

The pressure drop predictions for non-Newtonian fluids made by both the1-D method and the computational fluid dynamics method, using k and nvalues obtained from low shear Brookfield viscometer testing, aresignificantly lower than the measured experimental pressure drop (asshown in FIGS. 57-59). Also the discrepancy between the predictions andmeasurements increases as the viscosity of the non-Newtonian fluidincreases.

The Brookfield viscometer estimates the viscosity of the non-Newtonianfluid between 0.1 and 100 sec⁻¹ shear rate. This range of shear rates isused to estimate the power law relationship between the viscosity andshear rate. However, as shown in FIGS. 57-59, the shear rates in thetest device are in the range from 5000 to 50,000 sec⁻¹. These highershear rates are typical for operation in a microchannel emulsificationdevice. The discrepancy between the predicted and the measured pressuredrop indicates that the power law relationship estimated by viscometermay not be adequate for accurate prediction of the pressure drop in amicrochannel.

Using the experimental pressure drop data, k and n values arerecalculated to match predictions with experimental pressure drop. Thenew values of k and n are significantly different from values estimatedby viscometer indicating a different viscosity-shear rate relationshipat high shear rates. Table 3 summarizes the comparison. FIG. 60 shows acomparison of experimental pressure drop and predictions using the new kand n values for the low viscosity fluid. The results for the medium andhigh viscosity fluid are similar and the error in predictions is lessthan 1%.

This apparent discrepancy is attributed to a change in the power lawrelationship of the non-Newtonian fluid between a low to high shear rateenvironment at microchannel dimensions. While not wishing to be bound bytheory, it is believed that the small channel dimensions and highthroughput in the microchannels may cause changes to the laminar fluidprofile. The increased value of n suggests that the velocity profile isfurther flattened. The effect of the flattened fluid profile mayincrease the apparent viscosity at the wall and results in higherpressure drop in the microchannel.

Further, additional experiments are performed in the tube viscometerunder low shear, and the resulting values of k and n match thatpredicted by the Brookfield viscometer in this low shear rate regime asshown in Table 4. The theorized relationship between viscosity and shearrate for power-law non-Newtonian fluid in a microchannel is shown inFIG. 61. At the transition shear rate, there is a change in theviscosity-shear rate relationship.

TABLE 3 Comparison of k and n values estimated by Brookfield viscometerand calculated from high shear experimental data Brookfield Estimationfrom Viscometer experimental data K n k n Low Viscosity 0.16 0.65 0.100.74 Medium Viscosity 0.55 0.49 0.28 0.68 High Viscosity 2.13 0.33 0.660.62

TABLE 4 Comparison of k and n values estimated by Brookfield viscometerand calculated from low shear experimental tube data BrookfieldEstimation from Viscometer experimental data k n k N Medium Viscosity0.55 0.49 0.53 0.55

The power law relationship between viscosity and shear rate for a shearthinning non-Newtonian fluid estimated by a laboratory viscometer isgenerally in the low shear rate range. The high velocity shear-thinningnon-Newtonian flow through microchannels with small characteristicsdimensions results in high shear rates. At these high shear rates, thepower law estimated by the low shear laboratory viscometer may not beaccurate for pressure drop predictions. Good predictive pressure dropmodels for micro-channel dimensions may be obtained for non-Newtonianfluids by the foregoing pressure drop test with fluid and flow rates inthe region of interest. The models developed by this method may be usedfor accurate predictions and system design. Further, the results suggestthat the fluid profile within the narrow channel changes in a high shearenvironment, such that the apparent viscosity increases.

Though the difference between the viscosity-shear rate relationshipextrapolated from a viscometer measurements and the actualviscosity-shear rate relationship for high shear rate flow inmicrochannels is observed for shear-thinning fluid. It is possible thatfor other types of non-Newtonian fluids such as shear-thickening,time-dependent fluid (thixotropic, rheopectic), viscometer measurementsat low shear rates may not be applicable for high shear rate flow inmicrochannels.

Utilization of the accurate pressure drop models discussed here may beused to design processes and apparatuses using a plurality ofmicrochannels in a microchannel processing unit or a module for amicrochannel processing unit. The fluid introduced into one microchannelprocessing unit may flow through a manifold section and then into aplurality of microchannels. Channel dimensions and flow restrictions maybe selected using the models to obtain sufficient flow distributionamong to channels to obtain the desired result of unit operations beingperformed in the device. Unit operations may include reactions,separations, heating, cooling, vaporization, condensation, mixing, andthe like. One measure of flow distribution is the Quality Index Factor.The Quality Index Factor “Q₁” may be a measure of how effective amanifold is in distributing flow. It is the ratio of the differencebetween the maximum and minimum rate of connecting channel flow dividedby the maximum rate. For systems of connecting channels with constantchannel dimensions it may be desired to achieve equal mass flow rate perchannel. The equation for this case may be as follows:

$Q_{1} = {\frac{m_{\max} - m_{\min}}{m_{\max}} \times 100\%}$

wherem_(max) [kg/sec]=maximum connecting channel mass flow ratem_(min) [kg/sec]=minimum connecting channel mass flow rateFor cases where there are varying connecting channel dimensions it maybe desired that the residence time, contact time, velocity or mass fluxrate have minimal variation from channel to channel such that therequired duty of the unit operation may be attained. For those cases theQuality Index Factor may be defined as:

${Q_{2} = {\frac{G_{\max} - G_{\min}}{G_{\max}} \times 100\%}},$

where G is the mass flux rate. For cases when all the connectingchannels have the same cross sectional area, the equation for Q₂simplifies to Q₁. The Quality Index Factor gives the range of connectingchannel flow rates, with 0% being perfect distribution, 100% showingstagnation (no flow) in at least one channel, and values of over 100%indicating backflow (flow in reverse of the desired flow direction) inat least one channel. Q₁ and Q₂ may be defined based on the channelsthat comprise about 95% of the net flow through the connecting channelswherein the lowest flow channels are not counted if the flow throughthose channels is not needed to account for about 95% of the net flowthrough the connecting channels. The Quality Index Factor may be about20% or less, and in one embodiment about 5% or less, and in oneembodiment about 1% or less. In one embodiment, the Quality Index Factormay be in the range from about 0.5% to about 5%.

While the invention has been explained in relation to specificembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventioncovered herein is intended to include such modifications as may fallwithin the scope of the appended claims.

1. A process, comprising: conducting unit operations in at least twoprocess zones in a process microchannel to treat and/or form anon-Newtonian fluid, a different unit operation being conducted in eachprocess zone; and applying an effective amount of shear stress to thenon-Newtonian fluid to reduce the viscosity of the non-Newtonian fluidin each process zone, the average shear rate in one process zonediffering from the average shear rate in another process zone by afactor of at least about 1.2; wherein the unit operations are selectedfrom heating the non-Newtonian fluid, cooling the non-Newtonian fluid,forming the non-Newtonian fluid by mixing two or more fluids, contactingand/or mixing the non-Newtonian fluid with one or more other fluidsand/or particulate solids, conducting a reaction using two or morefluids to form a non-Newtonian fluid, conducting a reaction using as thereactant one or more non-Newtonian fluids, condensing the non-Newtonianfluid, vaporizing the non-Newtonian fluid, separating one or morecomponents from the non-Newtonian fluid, or a combination of two or morethereof.
 2. The process of claim 1 wherein the average shear rate in atleast one process zone is in excess of about 100 sec⁻¹.
 3. The processof claim 1 wherein the process microchannel has a convergingcross-sectional area in at least one process zone, the shear stressbeing applied to the non-Newtonian fluid by flowing the non-Newtonianfluid through the converging cross-sectional area.
 4. The process ofclaim 1 wherein the process microchannel comprises surface features onand/or in one or more interior surfaces in at least one process zone,the shear stress being applied to the non-Newtonian fluid by flowing thenon-Newtonian fluid in contact with the surface features.
 5. The processof claim 1 wherein the process microchannel comprises one or moreinterior structured walls in at least one process zone, the shear stressbeing applied to the non-Newtonian fluid by flowing the non-Newtonianfluid in contact with one or more structured walls.
 6. The process ofclaim 1 wherein the process microchannel comprises one or more internalobstructions in at least one process zone, the shear stress beingapplied to the non-Newtonian fluid by flowing the non-Newtonian fluid incontact with one or more internal obstructions.
 7. The process of claim1 wherein the viscosity of the non-Newtonian fluid in at least oneprocess zone is reduced to a viscosity of up to about 10⁵ centipoise. 8.The process of claim 1 wherein the non-Newtonian fluid comprises atleast one polymer, polymer composition, multiphase fluid mixture oremulsion.
 9. The process of claim 1 wherein the non-Newtonian fluidcomprises at least one polymer, the polymer comprising repeating unitsderived from one or more polymerizable olefins, cyclic olefins, dienes,ethers, esters, amides, carbonates, acetates, acrylics, alkylacrylics,acrylates, alkylacrylates, vinyl acetate, styrene, vinyls, vinylidenes,acrylonitrite, cyanoacrylates, tetrafluoroethylene, and combinations oftwo or more thereof.
 10. The process of claim 1 wherein thenon-Newtonian fluid comprises at least one polymer, the polymercomprising polyethylene, polypropylene, polystyrene, rubber modifiedpolystyrene, styrene-butadiene copolymer, vinyl polymer, vinylcopolymer, acrylonitrile-butadiene-styrene copolymer,polymethylmethacrylate, polycarbonate, or a mixture of two or morethereof.
 11. The process of claim 1 wherein the non-Newtonian fluidcomprises at least one polymer, the polymer being derived from ethyleneand/or propylene, and one or more monomers comprising acrylate,alkylacrylate, acrylic acid, alkylacrylic acid and/or vinyl acetate. 12.The process of claim 1 wherein the non-Newtonian fluid comprises atleast one polymer, the polymer comprising natural rubber, reclaimedrubber, synthetic rubber, or a mixture of two or more thereof.
 13. Theprocess of claim 1 wherein the non-Newtonian fluid comprises at leastone polymer, the polymer comprising one or more polymers of acrylic acidcrosslinked with one or more polyakenyl polyethers.
 14. The process ofclaim 1 wherein the non-Newtonian fluid comprises a multiphase mixture,the multiphase mixture comprising water and/or at least one organicliquid.
 15. The process of claim 1 wherein non-Newtonian fluid comprisesa multiphase mixture, the multiphase mixture comprising at least oneliquid hydrocarbon.
 16. The process of claim 1 wherein the non-Newtonianfluid comprises a multiphase mixture, the multiphase mixture comprisingat least one natural oil, synthetic oil, or mixture thereof.
 17. Theprocess of claim 1 wherein the non-Newtonian fluid comprises amultiphase mixture, the multiphase mixture comprising one or more:emulsifiers; surfactants; UV protection factors; waxes; consistencyfactors; thickeners; superfatting agents; stabilizers; cationic,anionic, zwitterionic, amphoteric or nonionic polymers; siliconecompounds; fats; waxes; lecithins; phospholipids; biogenic agents;antioxidants; deodorants; antiperspirants; antidandruff agents; swellingagents; insect repellents; self-tanning agents; tyrosine inhibitors;solubilizers; preservatives; perfume oils; or dyes; or a mixture of twoor more thereof.
 18. The process of claim 1 wherein the non-Newtonianfluid comprises a multiphase mixture, solids being dispersed in themultiphase mixture.
 19. The process of claim 1 wherein a first fluid anda second fluid are in the process microchannel; the first fluid, secondfluid, mixture of the first fluid and second fluid, and/or product madeby reacting the first fluid with the second fluid being a non-Newtonianfluid.
 20. The process of claim 1 wherein the non-Newtonian fluidcomprises a mixture of at least one first fluid and at least one secondfluid or a product made by reacting at least one first fluid with atleast one second fluid, at least one staged addition channel beingadjacent to the process microchannel and at least one apertured sectionbeing positioned between the at least one staged addition channel andthe process microchannel, the first fluid flowing in the processmicrochannel, the second fluid flowing from the at least one stagedaddition channel through the at least one apertured section into atleast one process zone in the process microchannel in contact with thefirst fluid.
 21. The process of claim 1 wherein the process microchannelis formed from parallel spaced sheets and/or plates.
 22. The process ofclaim 20 wherein the process microchannel and the staged additionchannel are formed from parallel spaced sheets and/or plates, theprocess microchannels and staged addition channels being positionedside-by-side or stacked one above another.
 23. The process of claim 1wherein the process microchannel exchanges heat with at least one heatexchange channel, the process microchannel and heat exchange channelbeing formed from parallel spaced sheets and/or plates, the heatexchange channel being adjacent to and/or in thermal contact with theprocess microchannel.
 24. The process of claim 20 wherein the aperturedsection comprises at least one sheet and/or plate with a plurality ofapertures in the sheet and/or plate.
 25. The process of claim 20 whereinthe apertured section is made from a porous material.
 26. The process ofclaim 1 wherein heat is exchanged between the process microchannel and aheat source and/or heat sink.
 27. The process of claim 26 wherein theheat source and/or heat sink comprises at least one heat exchangechannel.
 28. The process of claim 27 wherein a heat exchange fluid is inthe heat exchange channel.
 29. The process of claim 26 wherein the heatsource and/or heat sink comprises an electric heating element, aresistance heater and/or a non-fluid cooling element.
 30. The process ofclaim 4 wherein the surface features are in the form of depressions inand/or projections from one or more of the microchannel interior wallsthat are oriented at oblique angles relative to the direction of flow offluid through the microchannel.
 31. The process of claim 4 wherein thesurface features are in the form of at least two surface feature regionswherein mixing of the first fluid and second fluid is conducted in afirst surface feature region followed by flow in a second surfacefeature region wherein the flow pattern in the second surface featureregion is different than the flow pattern in the first surface featureregion.
 32. The process of claim 1 wherein the non-Newtonian fluid is areactant and/or a product in a chemical reaction, the reaction being agas-liquid reaction, liquid-liquid reaction, gas-liquid-liquid reaction,gas-liquid-solid reaction, or a liquid-liquid-solid reaction.
 33. Theprocess of claim 1 wherein the non-Newtonian fluid is a reactant and/ora product in a chemical reaction, the reaction being an oxidationreaction, hydrocracking reaction, hydrogenation reaction, hydrationreaction, carbonylation reaction, sulfation reaction, sulfonationreaction, oligomerization reaction or polymerization reaction.
 34. Theprocess of claim 1 wherein at least one unit operation comprises achemical reaction wherein the non-Newtonian fluid is a reactant and/or aproduct, the chemical reaction being conducted in the presence of acatalyst.
 35. The process of claim 34 wherein the catalyst comprises ahomogeneous catalyst, or is in the form of particulate solids, iswashcoated on one or more interior surfaces of the process microchannel,or is grown on one or more interior surfaces of the processmicrochannel.
 36. The process of claim 34 wherein the catalyst issupported by a support, the support being made of a material comprisingone or more of silica gel, foamed copper, sintered stainless steelfiber, steel wool, alumina, poly(methyl methacrylate), polysulfonate,poly(tetrafluoroethylene), iron, nickel sponge, nylon, polyvinyl idenedifluoride, polypropylene, polyethylene, polyethylene ethylketone,polyvinyl alcohol, polyvinyl acetate, polyacrylate,polymethylmethacrylate, polystyrene, polyphenylene sulfide, polysulfone,polybutylene, or a combination of two or more thereof.
 37. The processof claim 34 wherein the catalyst comprises a heat conductive material.38. The process of claim 34 wherein the catalyst is supported on asupport having a flow-by configuration, a flow-through configuration, ahoneycomb structure or a serpentine configuration.
 39. The process ofclaim 34 wherein the catalyst is supported on a support, the supportbeing in the form of a foam, felt, wad, fin, or a combination of two ormore thereof.
 40. The process of claim 34 wherein the catalyst issupported on a support, the support comprising a fin assembly comprisingat least one fin.
 41. The process of claim 34 wherein the catalyst issupported on a support, the support comprising a microgrooved supportstrip.
 42. The process of claim 1 wherein the process is conducted in amicrochannel processing unit comprising one or more inlet manifolds anda plurality of the process microchannels, the process comprising flowinga Newtonian and/or non-Newtonian fluid through the one or more inletmanifolds and distributing the Newtonian and/or non-Newtonian fluid tothe plurality of process microchannels, the Quality Index Factor beingless than about 20%.
 43. The process of claim 1 wherein the process isconducted in a microchannel processing unit comprising a plurality ofthe process microchannels, the process comprising flowing thenon-Newtonian fluid in the plurality of process microchannels, the shearrate of the non-Newtonian fluid in the process microchannels being inexcess of about 100 sec⁻¹, the shear force deviation factor being lessthan about
 2. 44. The process of claim 1 wherein the process isconducted in a microchannel processing unit comprising an inlet manifoldand a plurality of the process microchannels, the process comprisingflowing a non-Newtonian fluid through the manifold and distributing thenon-Newtonian fluid to the plurality of process microchannels, thenon-Newtonian fluid flowing straight through the inlet manifold withoutmaking any turns in the manifold.
 45. The process of claim 1 wherein theprocess is conducted in a microchannel processing unit comprising aninlet manifold and a plurality of the process microchannels, the processcomprising flowing a Newtonian fluid through the manifold anddistributing the Newtonian fluid to the plurality of processmicrochannels, the Newtonian fluid flowing into the inlet manifold andmaking at least one turn in the inlet manifold prior to entering theprocess microchannels.
 46. The process of claim 1 wherein the process isconducted in a microchannel processing unit comprising an inlet manifoldand a plurality of the process microchannels, the process comprisingflowing a feed stream through the inlet manifold and distributing thefeed stream to the plurality of process microchannels, the feed streamcontacting flow resistors in the inlet manifold.
 47. The process ofclaim 1 wherein the process is conducted in a microchannel processingunit comprising an inlet manifold and a plurality of the processmicrochannels, the process comprising flowing a feed stream through theinlet manifold and distributing the feed stream to the plurality ofprocess microchannels, the feed stream flowing through flow distributionfeatures.
 48. The process of claim 1 wherein the average shear rate inone process zone differs from the average shear rate in another processzone by a factor of at least about 1.5.
 49. The process of claim 1wherein the average shear rate in one process zone differs from theaverage shear rate in another process zone by a factor of at least about2.